WO2022176869A1 - Method for producing permanent film, method for producing multilayer body, and method for producing semiconductor device - Google Patents
Method for producing permanent film, method for producing multilayer body, and method for producing semiconductor device Download PDFInfo
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- WO2022176869A1 WO2022176869A1 PCT/JP2022/006037 JP2022006037W WO2022176869A1 WO 2022176869 A1 WO2022176869 A1 WO 2022176869A1 JP 2022006037 W JP2022006037 W JP 2022006037W WO 2022176869 A1 WO2022176869 A1 WO 2022176869A1
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- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- XLRPYZSEQKXZAA-OCAPTIKFSA-N tropane Chemical compound C1CC[C@H]2CC[C@@H]1N2C XLRPYZSEQKXZAA-OCAPTIKFSA-N 0.000 description 1
- 229930004006 tropane Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
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- C08F290/144—Polymers containing more than one epoxy group per molecule
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- the present invention relates to a permanent film manufacturing method, a laminate manufacturing method, and a semiconductor device manufacturing method.
- Patent Document 1 discloses a fine pattern forming resin composition containing a resin containing a hydroxyl group, a cross-linking component, and an alcohol solvent, wherein the fine pattern forming resin composition contains a compound having a specific structure as the cross-linking component. is described.
- Patent Document 2 discloses a resist pattern microstructure comprising an aqueous solution containing a copolymer of (A) vinylpyrrolidone and (B) at least one monomer selected from among water-soluble vinyl compounds other than component (A).
- a coating-forming agent for curing is described.
- the present invention provides a method for producing a permanent film capable of forming a fine pattern of the permanent film, a method for producing a laminate including the method for producing the permanent film, and a method for producing the permanent film or production of the laminate. It is an object of the present invention to provide a method of manufacturing a semiconductor device, including a method.
- a second resin composition is applied onto the substrate having the first pattern, and a coating of the second resin composition is formed on the first pattern and on the region between the first patterns. process, and removing a portion of the coating of the second resin composition to form a second pattern in contact with the first pattern;
- the area between the patterns in the composite pattern consisting of the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.
- ⁇ 2> The method for producing a cured film according to ⁇ 1>, wherein the first resin composition is a negative radiation-sensitive resin composition.
- the step of obtaining the base material having the first pattern is a step of selectively exposing the first resin composition film and then developing by solvent development;
- Any one of ⁇ 1> to ⁇ 3>, wherein the step of forming the second pattern is a step of removing part of the film of the second resin composition by solvent development.
- method for producing a permanent film of ⁇ 5> After the step of forming the coating of the second resin composition and before the step of forming the second pattern, the first pattern and the coating of the second resin composition are heated.
- ⁇ 6> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 5>, wherein the second resin composition contains a thermal polymerization initiator.
- ⁇ 7> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 6>, wherein the second resin composition contains a resin having a polymerizable group.
- ⁇ 8> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 7>, wherein the second resin composition contains a compound having a polymerizable group and a fluorene ring structure.
- ⁇ 9> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 8>, wherein the resin contained in the first resin composition is a polyimide precursor or a polybenzoxazole precursor.
- the resin contained in the first resin composition is a polyimide precursor or a polybenzoxazole precursor.
- ⁇ 10> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 9>, wherein the resin contained in the second resin composition is a polyimide precursor or a polybenzoxazole precursor.
- ⁇ 11> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 10>, wherein the obtained permanent film contains polyimide or polybenzoxazole.
- ⁇ 12> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 11>, further including a heating step after the step of forming the second pattern.
- ⁇ 13> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 12>, wherein the composite pattern has an elongation at break of 40% or more.
- ⁇ 14> The method for producing a permanent film according to any one of ⁇ 1> to ⁇ 13>, wherein the first pattern includes at least one of a hole pattern and a trench pattern.
- ⁇ 15> A method for producing a laminate, including the method for producing a permanent film according to any one of ⁇ 1> to ⁇ 14>.
- ⁇ 16> A method for manufacturing a semiconductor device, including the method for manufacturing a permanent film according to any one of ⁇ 1> to ⁇ 14> or the method for manufacturing a laminate according to ⁇ 15>.
- a method for producing a permanent film capable of forming a fine pattern of the permanent film a method for producing a laminate including the method for producing the permanent film, and a method for producing the permanent film or the laminate
- a method of fabricating a semiconductor device including a method of fabricating a.
- a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
- the term "process” is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
- a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
- alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
- Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- (meth)acrylate means both or either of “acrylate” and “methacrylate”
- (meth)acrylic means both “acrylic” and “methacrylic”
- (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
- Me in the structural formulas represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- total solid content refers to the total mass of all components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
- THF tetrahydrofuran
- NMP N-methyl-2-pyrrolidone
- detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
- UV ray ultraviolet
- a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
- the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
- the composition may contain two or more compounds corresponding to each component contained in the composition.
- the content of each component in the composition means the total content of all compounds corresponding to that component.
- the temperature is 23° C.
- the pressure is 101,325 Pa (1 atm)
- the relative humidity is 50% RH unless otherwise specified. Combinations of preferred aspects are more preferred aspects herein.
- the method for producing a permanent film of the present invention includes a step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern; A step of applying a second resin composition on a substrate having a pattern of and forming a coating of the second resin composition on the first pattern and on the area between the first patterns; , removing a portion of the coating of the second resin composition to form a second pattern in contact with the first pattern, wherein the first pattern is less than the area between the patterns in the first pattern. and the second pattern, the area between the patterns is narrower.
- the resin composition is patterned by exposure and development, or by forming a resist pattern on the resin composition and etching the resin composition using the resist pattern as a mask.
- the limits of the exposure wavelength used for exposure, etc. there was a limit to miniaturization of the pattern.
- the area between the patterns in the composite pattern consisting of the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.
- fine permanent film patterns for example, fine hole patterns, fine trench patterns, etc.
- the thickness of the pattern itself can be increased as compared with the case where only the first pattern is formed. Therefore, it is also possible to increase the aspect ratio of the pattern.
- the first resin composition contains a resin having a polymerizable group
- the second resin composition contains a component having a polymerizable group (a resin having a polymerizable group, a polymerizable compound, etc.)
- the reliability of the pattern means that peeling is unlikely to occur between the substrate and the pattern even after a long period of time.
- Patent Documents 1 and 2 do not describe manufacturing fine patterned permanent films.
- FIG. 1(a) shows an example of a substrate having a first pattern 2 on the substrate 1.
- FIG. 1(a) a first pattern 2 is formed on a substrate 1, and an inter-pattern region 4 (region where no pattern exists) is formed between two first patterns.
- FIG. 1(b) shows an example of a state in which a film of the second resin composition is formed on the first pattern and on the regions between the first patterns.
- a coating 6 of the second resin composition is formed on the first pattern 2 and in the region 4 between the patterns.
- FIG. 1(c) shows a region 8 where the film of the second resin composition is removed when part of the film of the second resin composition shown in FIG.
- FIG. 1(d) shows an example of a state in which part of the coating of the second resin composition is removed.
- the region 8 in FIG. 1(c) is removed, and a composite pattern consisting of a first pattern 2 and a second pattern 10 is formed in FIG. 1(d).
- the first pattern 2 and the second pattern 10 are shown separately, but these may be integrated by covalent bonding of components contained in each pattern.
- the area 12 between the patterns of the composite pattern in FIG. 1(d) is narrower than the area 4 between the patterns in FIG. 1(a).
- the area between patterns can be narrowed compared to the case where the pattern is formed only by the first pattern. That is, fine patterns can be formed.
- each step included in the method for producing a permanent film of the present invention will be described in detail.
- the method for producing a permanent film of the present invention includes a step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern ("first Also referred to as "pattern formation step”.). The details of the first resin composition will be described later.
- the first pattern forming step preferably includes a first film forming step of applying the first resin composition onto the substrate to form a film.
- the first pattern forming step includes the first film forming step, a first exposure step of selectively exposing the film formed by the first film forming step, and exposure by the first exposure step. It is more preferable to include a first developing step of developing the coated film with a developer to form a pattern.
- the step of obtaining the base material having the first pattern is preferably a step of selectively exposing the first resin composition film and then developing it by solvent development.
- Solvent development refers to development using a developer containing an organic solvent, which will be described later. That is, the first resin composition film is preferably a photosensitive film subjected to exposure and development, and preferably a photosensitive film subjected to exposure and development using a developer containing an organic solvent.
- the first resin composition film may be a photosensitive film subjected to positive development or a photosensitive film subjected to negative development. A photosensitive film is more preferable.
- negative development refers to development in which non-exposed areas are removed
- positive development refers to development in which exposed areas are removed.
- the first pattern forming step includes the first film forming step, the first exposing step, the first developing step, and a first step of heating the pattern obtained by the first developing step. It is particularly preferred to include at least one of a first post-development exposure step of exposing the pattern obtained by the heating step and the developing step.
- the first pattern preferably includes at least one of a hole pattern (eg, via pattern) and a trench pattern.
- a hole pattern for example, a hole pattern with a diameter of 0.5 to 100 ⁇ m can be mentioned, and a hole pattern with a diameter of 3 to 50 ⁇ m is preferable.
- the shape of the holes is not particularly limited, for example, a hole pattern having a circular shape when viewed from above can be used.
- the diameter of the hole pattern is the diameter of the circle
- the diameter of the hole pattern is the circle of the shape of the hole pattern when viewed from above. It means an equivalent diameter (in a shape with a certain area, the diameter of a circle that has the same area as that area).
- the trench pattern for example, a trench pattern with a trench width of 0.5 to 100 ⁇ m can be mentioned, and a trench pattern with a trench width of 3 to 50 ⁇ m is preferable.
- the film thickness of the first pattern is preferably 1 to 50 ⁇ m, more preferably 2 to 20 ⁇ m, even more preferably 3 to 15 ⁇ m.
- the method for producing a permanent film of the present invention preferably includes a first film forming step of applying the first resin composition onto a substrate to form a film.
- the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
- semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.
- a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
- these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
- HMDS hexamethyldisilazane
- the shape of the substrate is not particularly limited, and may be circular or rectangular.
- the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
- the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
- the base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
- the resin layer or metal layer serves as the base material.
- Coating is preferable as a means for applying the first resin composition onto the substrate.
- Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
- a film having a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the first resin composition according to the method.
- the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, ink jet method, etc.
- slit coating and spray coating are preferable for rectangular substrates.
- method, inkjet method, and the like are preferred.
- spin coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
- a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
- the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
- a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
- EBR edge bead rinsing
- a pre-wetting step is employed in which various solvents are applied to the base material before applying the first resin composition to the base material to improve the wettability of the base material, and then the first resin composition is applied.
- the first pattern forming step may include a first drying step of drying the film formed by the first film forming step. Also, the first drying step is preferably performed after the first film forming step and before the first exposure step.
- the drying temperature of the film in the first drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
- the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
- the method for producing a permanent film of the present invention may include a first exposure step of selectively exposing the film formed by the first film forming step.
- Selectively exposing means exposing a portion of the film.
- the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
- the amount of exposure is not particularly defined as long as it can sensitize the first resin composition. is more preferred.
- the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
- the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
- semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355
- the method of exposure is not particularly limited as long as at least a part of the film made of the first resin composition is exposed. mentioned.
- the film may be subjected to a step of heating after exposure (first post-exposure heating step). That is, the method for producing a permanent film of the present invention may include a first post-exposure heating step of heating the film exposed by the first exposure step.
- the first post-exposure heating step can be performed after the first exposure step and before the first development step.
- the heating temperature in the first post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
- the heating time in the first post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
- the heating rate in the first post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and further preferably 3 to 10° C./min from the temperature at the start of heating to the maximum heating temperature. preferable. Also, the rate of temperature increase may be appropriately changed during heating.
- the heating means in the first post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. It is also preferable to perform the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
- the film after exposure may be subjected to a first development step in which the film is developed using a developer to form a pattern.
- the method for producing a permanent film of the present invention may include a first development step of developing the film exposed in the first exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
- development in which the unexposed portion of the film is removed by the development process is called negative development
- development in which the exposed portion of the film is removed by the development process is called positive development.
- Examples of the developer used in the first development step include a developer containing an alkaline aqueous solution or an organic solvent.
- basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
- TMAH tetramethylammonium hydroxide
- potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide , butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)am
- the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
- the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g.
- methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl
- methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g.
- ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate
- the organic solvent can be used singly or in combination of two or more.
- a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
- the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
- the developer may further contain other components.
- Other components include, for example, known surfactants and known antifoaming agents.
- the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle.
- the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
- the method of supplying with a spray nozzle is more preferable.
- the substrate is spun to remove the developer from the substrate.
- a step of removing from above may be employed, and this step may be repeated multiple times.
- the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
- a process of vibrating with sound waves or the like and a process of combining them can be employed.
- the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
- the pattern may be washed (rinsed) with a rinse.
- a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the developer is an alkaline aqueous solution
- water for example, can be used as the rinse.
- a solvent different from the solvent contained in the developer for example, water, an organic solvent different from the organic solvent contained in the developer
- the rinse liquid is used as the rinse liquid. be able to.
- the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3- methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g.
- methyl 2-alkyloxypropionate 2 -ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acid)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g.
- ethers such as diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether a
- the organic solvent can be used singly or in combination of two or more.
- the organic solvent can be used singly or in combination of two or more.
- cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
- the rinse liquid contains an organic solvent
- the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
- the rinse solution may further contain other components.
- Other components include, for example, known surfactants and known antifoaming agents.
- Rinse liquid supply method The method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed. There is a method of continuously supplying the rinsing liquid onto the material using means such as a straight nozzle. From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable.
- the rinsing step is preferably a step of supplying the rinse liquid to the pattern after the development through a straight nozzle or a step of continuously supplying the rinse liquid, and more preferably a step of supplying the rinse liquid through a spray nozzle.
- the method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be employed.
- the rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
- the pattern obtained by the first developing step may be subjected to the first heating step of heating the pattern obtained by the above developing. That is, the method for producing a permanent film of the present invention may include a first heating step of heating the pattern obtained by the first developing step. In addition, the method for producing a permanent film of the present invention includes a first heating step of heating the pattern obtained by another method without performing the developing step or the film obtained by the first film forming step. It's okay.
- the heating temperature (maximum heating temperature) in the first heating step is preferably 50 to 200°C, more preferably 60 to 160°C, still more preferably 70 to 150°C, even more preferably 80 to 140°C, and 90 to 120°C. °C is particularly preferred.
- Heating in the first heating step is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12° C./min.
- the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
- By setting the temperature increase rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
- the residual stress of the object can be relaxed.
- the temperature at the start of heating is preferably 20-120°C, more preferably 20-100°C, and even more preferably 20-80°C.
- the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started. For example, it is the temperature of the film (layer) after development (or after rinsing). For example, it is preferable to raise the temperature from a temperature 30 to 200° C. lower than the boiling point of the solvent contained in the first resin composition.
- the heating time (heating time at the maximum heating temperature) is preferably 30 seconds to 120 minutes, more preferably 60 seconds to 60 minutes, even more preferably 90 seconds to 30 minutes.
- Heating may be done step by step. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
- the first heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
- the heating means in the first heating step is not particularly limited, but includes, for example, a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
- the pattern obtained by the first developing step (pattern after rinsing when performing the rinsing step) is replaced with the first heating step or in addition to the first heating step after the developing step. may be subjected to a first post-development exposure step that exposes a pattern of . That is, the method for producing a permanent film of the present invention may include a first post-development exposure step of exposing the pattern obtained by the first development step. The method for producing a permanent film of the present invention may include the first heating step and the first post-development exposure step, or may include only one of the first heating step and the first post-development exposure step.
- the first post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator. etc. can be promoted.
- the first post-development exposure step at least part of the pattern obtained in the first development step may be exposed, but it is preferable to expose the entire pattern.
- the exposure amount in the first post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength at which the photosensitive compound exhibits sensitivity. is more preferable.
- the first post-development exposure step can be performed using, for example, the light source in the first exposure step described above, and broadband light is preferably used.
- the first pattern forming step includes another film forming step after the first film forming step, and the film obtained by the other film forming step is patterned by exposure, development, or the like, and then the pattern is formed. It is also preferable that the step of forming the first pattern by an etching process using the as a mask.
- a method of patterning the film obtained by other film forming steps by exposure, development, etc. the same methods as the above-described first exposure step and first development step can be mentioned.
- Etching can be performed with reference to known methods.
- the etching may be dry etching or wet etching, but dry etching is preferable.
- the pattern used as the mask may remain or be removed by the etching, but is preferably removed.
- the second resin composition is applied onto the substrate having the first pattern, and the first pattern is formed on the first pattern and in the region between the first patterns. 2 (hereinafter also referred to as “second resin composition film”) (second film forming step).
- the second film-forming step can be performed in the same manner as the first film-forming step, except that the second resin composition is applied onto the substrate having the first pattern.
- a drying step similar to the first drying step may be included as the second drying step.
- a film of the second resin composition can be formed on the entire surface of the substrate and the first pattern.
- the coating of the second resin composition may be formed only on a part of the substrate and the first pattern.
- the thickness of the film of the second resin composition formed in the second film forming step is preferably 0.1 to 20 ⁇ m. More preferably ⁇ 10 ⁇ m.
- the method for producing a permanent film of the present invention includes the step of removing part of the film of the second resin composition to form a second pattern in contact with the first pattern.
- the second pattern may be in contact with at least part of the first pattern, but is preferably formed so as to cover at least the side surface of the first pattern.
- the second pattern may be formed on all side surfaces of the first pattern, or the second pattern may be formed only on some of the plurality of side surfaces of the first pattern. good too.
- the first pattern is formed so as to cover the upper surface and side surfaces thereof.
- removing the film of the second resin composition it is preferably removed until a part of the substrate is exposed. That is, it is preferable that the region from which the film of the second resin composition is removed includes at least a region where the first pattern does not exist.
- a pattern consisting of the second pattern and the first pattern is also called a composite pattern.
- the shape of the composite pattern is not particularly limited, but examples thereof include hole patterns (eg, via patterns), trench patterns, and the like.
- the shape of the composite pattern is preferably similar to the shape of the first pattern described above, except that the regions between the patterns are narrower.
- the above-described first pattern except for narrowing the region between the patterns.
- Composite patterns can be formed that are shaped like shapes. For example, if the first pattern is a hole pattern, the composite pattern is preferably a hole pattern with a smaller diameter than the first pattern.
- the diameter of the composite pattern, which is the hole pattern is preferably reduced by 0.1 ⁇ m or more, more preferably by 0.3 ⁇ m or more, with respect to the diameter of the first pattern, which is the hole pattern. Preferably, it is more preferably reduced by 0.5 ⁇ m or more.
- the composite pattern is a hole pattern
- a hole pattern with a diameter of 0.5 to 100 ⁇ m can be mentioned, and a hole pattern with a diameter of 3 to 50 ⁇ m is preferred.
- the definition of the diameter of the hole pattern is as described above.
- the composite pattern is preferably a trench pattern with a smaller trench width than the first pattern.
- the trench width of the composite pattern is preferably reduced by 0.1 ⁇ m or more, more preferably by 0.3 ⁇ m or more, with respect to the trench width of the first pattern, which is the trench pattern. is more preferable, and it is even more preferable to reduce by 0.5 ⁇ m or more.
- the composite pattern is a trench pattern
- a trench pattern with a trench width of 0.5 to 100 ⁇ m can be mentioned, and a trench pattern with a trench width of 3 to 50 ⁇ m is preferred.
- the film formed in the second film forming step (the film after the second preheating step when the second preheating step is included) is developed with a developer to form a pattern. It is preferred to include a second development step to form a
- the second development process can be performed by the same method as the first development process.
- first pattern forming step "first resin composition”, etc. in the first development step should be read as “second pattern forming step”, "second resin composition”, etc., respectively.
- the development time in the second development step is preferably 1 minute to 20 minutes, more preferably 2 minutes to 10 minutes.
- the step of forming the second pattern is preferably a step of removing part of the coating of the second resin composition by solvent development.
- Solvent development refers to development using a developer containing an organic solvent.
- ⁇ Second preheating step> In the method for producing a permanent film of the present invention, after the step of forming a film of the second resin composition and before the step of forming the second pattern, the first pattern and the second resin A step of heating the coating of the composition (second preheating step) may be included.
- the second preheating step for example, the solubility of the second resin composition film in the developer in the second developing step can be adjusted to facilitate formation of the composite pattern.
- Heating in the second preheating step can be performed, for example, by the same method as in the above-described first heating step.
- the heating temperature and heating time in the second preheating step may be determined according to the components contained in the second resin composition, the developer used in the second developing step, and the like.
- the heating temperature is preferably 80 to 180°C, more preferably 90 to 170°C.
- the method for producing a permanent film of the present invention further includes a heating step (second post-heating step) after the step of forming the second pattern.
- a heating step second post-heating step
- the polyimide precursor, the polybenzoxazole precursor, or the like The resin is cyclized to become a resin such as polyimide or polybenzoxazole.
- cross-linking of unreacted polymerizable groups in a resin or a compound having a polymerizable group other than a resin also progresses.
- the heating temperature (maximum heating temperature) in the second post-heating step is preferably 50 to 350°C, more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
- the second post-heating step is a step of promoting a cyclization reaction of the polyimide precursor or polybenzoxazole precursor in at least one of the first resin composition film and the second resin composition film by heating.
- Heating in the second post-heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
- the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
- the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 °C/sec is more preferred.
- the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
- the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started.
- the temperature after developing the second resin composition film for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the first resin composition or the second resin composition of the present invention. It is preferable to raise the temperature from the temperature.
- the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
- the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
- the upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.
- Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
- the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps.
- the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
- the second post-heating step is preferably performed in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
- the heating means in the second post-heating step is not particularly limited, but examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
- a second post-exposure step may be included instead of or in addition to the second post-heating step.
- the second post-exposure step can be performed in the same manner as the first post-development exposure step described above.
- the composite pattern obtained by the second pattern forming step may be subjected to a metal layer forming step of forming a metal layer on the composite pattern. That is, the method for producing a permanent film of the present invention preferably includes a metal layer forming step of forming a metal layer on the resulting composite pattern (preferably subjected to the second post-heating step).
- the metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
- the method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. can do.
- photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.
- a preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.
- the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m, at the thickest part.
- the permanent film (that is, composite pattern) obtained by the method for producing a permanent film of the present invention preferably contains polyimide or polybenzoxazole.
- at least one of the first pattern and the second pattern forming the permanent film should contain polyimide or polybenzoxazole, but both the first pattern and the second pattern may contain polyimide or polybenzoxazole.
- An embodiment containing oxazole is also one of the preferred embodiments of the present invention.
- the permanent film obtained by the manufacturing method of the permanent film of this invention contains a polyimide.
- at least one of the first pattern and the second pattern that form the permanent film may contain polyimide, but both the first pattern and the second pattern may contain polyimide. It is one of the preferred embodiments of
- Cyclized resins such as polyimide and polybenzoxazole are excellent in heat resistance, insulation, etc., so that permanent films containing such cyclized resins can be applied to various applications.
- the use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
- the elongation at break of the composite pattern obtained by the method for producing a permanent film of the present invention is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.
- the elongation at break can be measured by the method shown in Examples.
- the dielectric constant of the second resin composition under condition 1 below is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.
- the lower limit of the dielectric constant is not particularly limited, and may be 0 or more.
- the dielectric loss tangent of the second resin composition under condition 1 below is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
- the lower limit of the dielectric loss tangent is not particularly limited as long as it is 0 or more.
- Condition 1 The composition was applied to a silicon wafer having an oxide film (SiO 2 ) formed on the surface to a thickness of 15 ⁇ m, dried at 100° C. for 5 minutes, and heated at 230° C.
- the dielectric constant and dielectric loss tangent of a single film of the composition prepared by immersing it in hydrogen fluoride are measured.
- the dielectric constant and dielectric loss tangent can be measured according to JIS (Japanese Industrial Standards) R 1641 "Measuring method for microwave dielectric properties of fine ceramic substrates".
- Fields to which the method for producing a permanent film of the present invention or the permanent film obtained by the method for producing a permanent film of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films. etc.
- pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used. For these applications, for example, Science & Technology Co., Ltd.
- the method for producing a permanent film of the present invention or the permanent film obtained by the method for producing a permanent film of the present invention can be used for production of printing plates such as offset printing plates or screen printing plates, etching of molded parts, electronics, In particular, it can also be used, for example, for the production of protective lacquers and dielectric layers in microelectronics.
- laminate refers to a structure having a plurality of layers made of the permanent film obtained by the method for producing a permanent film of the present invention.
- the laminated body is a laminated body including two or more layers made of permanent films, and may be a laminated body in which three or more layers are laminated.
- all the layers made of the permanent film contained in the laminate may be layers made of the permanent film obtained by the method for producing a permanent film of the present invention. preferable.
- the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the permanent film of the present invention, and more preferably includes repeating the method for manufacturing the permanent film of the present invention multiple times.
- the laminated body of the present invention preferably includes two or more layers of permanent films, and preferably includes a metal layer between any of the layers of the permanent films.
- the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for manufacturing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the permanent film between the methods for manufacturing the permanent film that are performed multiple times. Preferred aspects of the metal layer forming step are as described above.
- the laminate for example, a laminate containing at least a layer structure in which three layers, a layer consisting of a first permanent film, a metal layer, and a layer consisting of a second permanent film are laminated in this order, is preferred. be done.
- both the layer comprising the first permanent film and the layer comprising the second permanent film are layers comprising a permanent film obtained by the method for producing a permanent film of the present invention.
- the resin composition used for forming the layer consisting of the first permanent film and the resin composition used for forming the layer consisting of the second permanent film may have the same composition. However, it may be a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.
- the method for manufacturing the laminate of the present invention includes a lamination step.
- the lamination step is to repeat (a) the first pattern formation step, (b) the second film formation step, and (c) the second pattern formation step on the surface of the composite pattern (permanent film) or metal layer. , in that order. If necessary, the above-described second preheating step, second postheating step, and the like may be further performed. In addition, (c) after the second pattern forming step (preferably after the second post-heating step), (d) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
- the lamination step when the lamination step is further performed, after the exposure step, after the (c) second pattern formation step (or after the second post-heating step), or (d) the metal
- a surface activation treatment step may be further performed after the layer forming step.
- a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
- the lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
- resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer, the number of resin layers (permanent film) is 2 or more and 20 or less.
- the structure is preferable, and the structure with 2 to 9 layers is more preferable.
- Each of the above layers may have the same composition, shape, film thickness, etc., or may differ from each other.
- a permanent film by the method for producing a permanent film of the present invention after providing the metal layer so as to cover the metal layer.
- the first pattern forming step, (b) the second film forming step, (c) the second pattern forming step, and (d) the metal layer forming step are repeated in this order. be done.
- the permanent film and the metal layer obtained by the method for producing the permanent film of the present invention are formed. They can be stacked alternately.
- the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least part of the metal layer and the permanent film.
- the surface activation treatment step is usually performed after the metal layer formation step, but after the second pattern formation step (c) (preferably after the second post-heating step), the permanent film is surface-activated.
- the metal layer forming step may be performed.
- the surface activation treatment may be performed only on at least a portion of the metal layer, may be performed on at least a portion of the permanent film, or may be performed on at least a portion of both the metal layer and the permanent film.
- the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which a permanent film is to be formed.
- the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which a permanent film is to be formed.
- the surface activation treatment include plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF 4 /O 2 . , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups and thiol groups.
- various source gases oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.
- corona discharge treatment corona discharge treatment
- NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 etching treatment surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups
- the treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound and mechanical surface roughening treatment using a brush.
- Plasma treatment is preferred, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferred.
- the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , most preferably 10,000-50,000 J/m 2 .
- the present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing the permanent film of the present invention or the method for manufacturing the laminate of the present invention.
- Specific examples of semiconductor devices using the permanent film obtained by the method for producing a permanent film of the present invention for forming an interlayer insulating film for a rewiring layer include the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and The description of FIG. 1 can be referred to, and the contents thereof are incorporated herein.
- first resin composition and second resin composition Components contained in the resin composition according to the present invention are described in detail below.
- the first resin composition and the second resin composition may be the same composition or different compositions.
- the first resin composition is preferably a negative radiation-sensitive resin composition.
- a negative radiation-sensitive resin composition is a composition used for forming a negative photosensitive film.
- the first resin composition is preferably a composition containing a resin and at least one of a photopolymerization initiator and a photoacid generator, and is a composition containing a resin and a photopolymerization initiator. More preferably, it is a resin containing a resin, a photopolymerization initiator, and a polymerizable compound.
- the resin contained in the first resin composition is preferably a polyimide precursor or a polybenzoxazole precursor.
- the second resin composition is preferably a thermosetting resin composition.
- the second resin composition preferably contains a thermal polymerization initiator.
- the second resin composition preferably contains a resin having a polymerizable group as the resin.
- the polymerizable group is preferably a group capable of forming polymerization with the resin contained in the first resin composition or the polymerizable compound.
- the primary resin composition contains a radically polymerizable compound
- the second resin composition preferably contains a resin having a radically polymerizable group.
- the resin contained in the second resin composition is preferably a polyimide precursor or a polybenzoxazole precursor.
- the resin contained in the first resin composition and the resin contained in the second resin composition are the same type of resin. It is also preferable that for example, there is a mode in which both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors. When both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors, the elongation at break of the obtained permanent film is considered to be improved.
- first resin composition The components contained in the first resin composition and the second resin composition are described in detail below.
- resin composition simply refers to both the first resin composition and the second resin composition.
- the resin composition according to the present invention contains a resin.
- resins include cyclized resins and their precursors (specific resins) and other resins shown below.
- the resin composition according to the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
- the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
- the main chain represents the relatively longest connecting chain in the resin molecule.
- cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
- a precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
- a resin that becomes a cyclized resin by forming a ring structure is more preferable.
- Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition according to the present invention includes, as the specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. resin (specific resin).
- the resin composition according to the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
- the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
- the resin composition according to the present invention preferably contains a radical polymerization initiator described later, and includes a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferable. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition according to the present invention.
- the specific resin may have a polarity conversion group such as an acid-decomposable group.
- the resin composition according to the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition according to the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
- polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
- a 1 and A 2 each independently represent an oxygen atom or -NH-
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
- a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
- R 111 in formula (2) represents a divalent organic group.
- divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom.
- may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
- Ar is each independently an aromatic group
- L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
- R 111 is preferably derived from a diamine.
- Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
- * represents a binding site with other structures.
- diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
- diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
- R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
- Ar is each independently an aromatic group
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
- Ar is preferably a phenylene group
- L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
- a divalent organic group represented by Formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
- the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
- R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
- Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
- R 111 contains a polycyclic aromatic ring structure.
- R 111 also preferably contains a polycyclic aromatic ring structure. According to this aspect, the dielectric constant of the permanent film can be lowered, and in some cases it is possible to suppress the increase in the electrical resistance of the wiring, the suppression of the decrease in the electrical resistance of the permanent film, and the like.
- Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. , but not limited to.
- R 111 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
- R 115 in formula (2) represents a tetravalent organic group.
- a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
- each * independently represents a binding site to another structure.
- R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
- R 115 contains a polycyclic aromatic ring structure.
- R 115 also preferably contains a polycyclic aromatic ring structure. According to this aspect, the dielectric constant of the permanent film can be lowered, and in some cases it is possible to suppress the increase in the electrical resistance of the wiring, the suppression of the decrease in the electrical resistance of the permanent film, and the like.
- Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. , but not limited to.
- R 115 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
- R 115 specifically includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
- the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types thereof, as the structure corresponding to R115 .
- the tetracarboxylic dianhydride is preferably represented by the following formula (O).
- R 115 represents a tetravalent organic group.
- the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
- tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
- R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
- R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
- the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
- At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
- the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
- the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
- a group having an ethylenically unsaturated bond is preferred.
- Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
- a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
- R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
- * represents a binding site with another structure.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
- R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
- alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
- a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
- the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
- the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
- the said alkylene group may have a substituent.
- Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
- the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
- a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
- the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
- the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
- tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
- R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
- the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
- acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
- the polyimide precursor preferably has a fluorine atom in its structure.
- the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
- the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
- a 1 and A 2 represent an oxygen atom
- R 111 and R 112 each independently represent a divalent organic group
- R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
- at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
- a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
- R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
- the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
- the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
- the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the multiple types of polyimide precursors as one resin are within the ranges described above.
- the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
- the alkali-soluble polyimide refers to a polyimide that dissolves at 23° C. by 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
- the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
- the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
- the polyimide preferably has a fluorine atom.
- a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
- the amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
- the polyimide preferably has a silicon atom.
- a silicon atom for example, is preferably contained in R131 in a repeating unit represented by formula (4) described later, and organically modified (poly)siloxane described later in R131 in a repeating unit represented by formula (4) described later More preferably included as a structure.
- the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
- the amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
- the polyimide preferably has an ethylenically unsaturated bond.
- the polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
- the ethylenically unsaturated bond preferably has radical polymerizability.
- the ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later.
- the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
- the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
- R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
- R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
- the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
- an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
- R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
- L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined
- X represents an oxygen atom or a sulfur atom
- * represents a bonding site with another structure
- ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
- a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
- X is preferably an oxygen atom.
- * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
- the structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
- the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
- the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
- a polyimide having a hydroxy group such as a phenolic hydroxy group
- a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
- * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
- the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
- Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
- Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
- a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
- the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
- the polyimide may have a polar conversion group such as an acid-decomposable group.
- the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
- Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described below, the terminal of polyimide, and the like.
- the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development” described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH.
- the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
- the acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
- the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka.
- pKa is a value calculated by ACD/ChemSketch (registered trademark).
- the acid group is a polyvalent acid such as phosphoric acid
- the pKa is the first dissociation constant.
- the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
- the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
- the polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
- a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
- the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
- the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
- R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
- the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
- R 133 is a polymerizable group, and other groups are the same as in formula (4).
- Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
- R 131 represents a divalent organic group.
- the divalent organic group are the same as those of R 111 in formula (2), and the preferred range is also the same.
- R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R 111 in formula (2) of the polyimide precursor.
- R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.
- Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
- R 132 represents a tetravalent organic group.
- examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
- four bonds of a tetravalent organic group exemplified as R 115 combine with four —C( ⁇ O)— moieties in the above formula (4) to form a condensed ring.
- R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
- a specific example is the example of R 115 in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
- R 131 and R 132 has an OH group. More specifically, R 131 is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. and more preferred examples of R 132 are the above (DAA-1) to (DAA-5).
- the polyimide preferably has a fluorine atom in its structure.
- the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
- the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably.
- monoamines examples include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzoic acid
- the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
- the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
- the imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
- the polyimide may contain repeating units represented by the above formula (4) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
- polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
- the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break). Also, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000. The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
- the upper limit of the polyimide molecular weight dispersion is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural kinds of polyimides as one resin are within the ranges described above.
- polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
- R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
- R 121 represents a divalent organic group.
- the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
- the aliphatic group a linear aliphatic group is preferred.
- R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
- a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
- the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred.
- the number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred.
- the linear aliphatic group is preferably an alkylene group.
- Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedi
- Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
- the dicarboxylic acid containing an aromatic group the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid consisting of only a group having an aromatic group and two -COOH is more preferable.
- A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.
- dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
- R 122 is also preferably a group derived from a bisaminophenol derivative.
- bisaminophenol derivatives having the following aromatic groups are preferred.
- X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
- R 122 is also preferably a structure represented by the above formula.
- any two of the total four * and # are binding sites with the nitrogen atom to which R 122 in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R 122 in formula (3) binds, or two * are binding sites to the nitrogen atom to which R 122 in formula (3) binds and two #s are more preferably a binding site to the oxygen atom to which R 122 in formula (3) binds, and two * are the oxygen to which R 122 in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R 122 in formula (3) is bonded.
- the bisaminophenol derivative is also preferably a compound represented by Formula (As).
- R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).
- R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
- R3 is a hydrogen atom , a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
- R 1 is alkylene or substituted alkylene.
- alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH 2 — and —CH(CH 3 ) -, -C(CH 3 ) 2 - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.
- the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of formula (3) above.
- the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
- Z has an a structure and a b structure
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
- At least one of R 3s , R 4s , R 5s and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
- Polymerization of a structure and b structure may be block polymerization or random polymerization.
- the mol % of the Z moiety is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.
- preferred Z include those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000.
- tetracarboxylic acid residues include those of R 115 in formula (2).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
- the molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
- the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
- the resin composition contains multiple types of polybenzoxazole precursors as specific resins
- the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the above plural kinds of polybenzoxazole precursors as one resin are within the ranges described above.
- Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.
- a radically polymerizable group is preferred.
- it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.
- R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
- the polar conversion group such as a polymerizable group or an acid-decomposable group
- the polar conversion group may be positioned at least one of R 133 and R 134 . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
- R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).
- the polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.
- R 133 represents a divalent organic group.
- Divalent organic groups include aliphatic groups and aromatic groups.
- a specific example is the example of R 121 in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R121 .
- R 134 represents a tetravalent organic group.
- Tetravalent organic groups include examples of R 122 in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of R122 .
- four bonds of a tetravalent organic group exemplified as R 122 combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring.
- R 134 when R 134 is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).
- Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more.
- the upper limit is not particularly limited, and may be 100%.
- the oxazolization rate is measured, for example, by the method described below.
- the infrared absorption spectrum of polybenzoxazole is measured, and the peak intensity Q1 near 1650 cm ⁇ 1 , which is the absorption peak derived from the amide structure of the precursor, is determined.
- the polybenzoxazole may contain repeating units of the above formula (X) that all contain one type of R 131 or R 132 , or may contain repeating units of the above formula (X) that contain two or more different types of R 131 or R 132 . ) repeating units.
- the polybenzoxazole may also contain other types of repeating units in addition to the repeating units of formula (X) above.
- Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
- a dicarboxylic acid an active ester type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.
- the weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000.
- the weight average molecular weight is particularly preferably 20,000 or more.
- the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
- the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
- the polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
- the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less.
- 2.2 or less is even more preferable.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are within the ranges described above.
- the polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
- R 117 represents a trivalent organic group
- R 111 represents a divalent organic group
- a 2 represents an oxygen atom or —NH—
- R 113 represents a hydrogen atom or a monovalent represents an organic group.
- R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
- the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
- preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
- the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
- R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
- a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
- the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.
- the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a Tricarboxylic acid compounds containing 6 to 20 aromatic groups or groups in which two or more of these are combined via a single bond or a linking group are preferred, and aromatic groups having 6 to 20 carbon atoms or carbon atoms via a single bond or linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.
- tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
- (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group
- Linked compounds and the like are included.
- These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
- R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, and preferred embodiments are also the same.
- Polyamideimide precursors may further comprise other repeating units.
- Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).
- R 116 represents a divalent organic group and R 111 represents a divalent organic group.
- R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
- the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
- preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
- the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
- R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
- a compound having two carboxy groups is called a dicarboxylic acid compound
- a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
- the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
- the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include acid dihalide compounds. One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
- the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
- a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms.
- dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9
- R 111 has the same definition as R 111 in formula (2) above, and preferred embodiments are also the same.
- the polyamideimide precursor preferably has a fluorine atom in its structure.
- the content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
- the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.
- An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1).
- the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
- the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
- the polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
- the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
- the polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
- the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution.
- a polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable.
- the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
- the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film to be obtained.
- the polyamideimide preferably has a fluorine atom.
- a fluorine atom is preferably contained in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R 117 or R 111 as a fluorinated alkyl group.
- the amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.
- the polyamideimide may have an ethylenically unsaturated bond.
- the polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, preferably in the side chain.
- the ethylenically unsaturated bond preferably has radical polymerizability.
- the ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and the repeating unit represented by formula (PAI-3) described later.
- R 117 or R 111 It is more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in .
- Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.
- the amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.
- Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
- the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the above polymerizable groups other than the ethylenically unsaturated bond in the polyimide.
- a polymerizable group other than an ethylenically unsaturated bond is preferably included in R 111 in a repeating unit represented by formula (PAI-3) described later, for example.
- the amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.
- -Polarity conversion group- Polyamideimide may have a polarity converting group such as an acid-decomposable group.
- the acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
- the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more is more preferable. Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
- the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, 3 ⁇ 30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
- the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
- the acid group contained in the polyamideimide the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.
- the polyamideimide preferably has a phenolic hydroxy group.
- Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
- a phenolic hydroxy group is preferably included in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later.
- the amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
- the polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).
- R 111 and R 117 have the same definitions as R 111 and R 117 in formula (PAI-2), and preferred embodiments are also the same.
- the polymerizable group may be located at least one of R 111 and R 117 , or may be located at the end of the polyamideimide.
- the main chain end of the polyamideimide is blocked with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
- a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
- Preferred aspects of the terminal blocker are the same as the preferred aspects of the terminal blocker in the polyimide described above.
- the imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
- the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
- the imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
- Polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R 111 or R 117 , and two or more different types of R 131 or R 132 . It may contain a repeating unit represented by the above formula (PAI-3). Moreover, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).
- Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or stopping the imidization reaction in the middle and partially imidizing the imide structure and a method of partially introducing an imide structure by blending a completely imidized polymer with its polyamideimide precursor.
- the weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
- the polyamidoimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
- the upper limit of the polyamidoimide molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.
- Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
- the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
- the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
- alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
- halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
- organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
- the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. is exemplified.
- a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
- One type of basic compound may be used, or two or more types may be used.
- the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
- terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
- Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
- Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
- Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
- Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable.
- Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. are mentioned.
- Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
- a step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
- the content of the specific resin in the resin composition according to the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. It is more preferable that the content is 50% by mass or more. Further, the content of the resin in the resin composition according to the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the resin composition. It is more preferably 97% by mass or less, even more preferably 95% by mass or less.
- the resin composition according to the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the resin composition according to the present invention preferably contains at least two resins.
- the resin composition according to the present invention may contain a total of two or more kinds of the specific resin and another resin described later, or may contain two or more kinds of the specific resin. It is preferable to include two or more kinds of.
- the resin composition according to the present invention contains two or more specific resins, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a polyimide precursor.
- the resin composition according to the present invention may contain, as a resin, a resin different from the specific resin (hereinafter also simply referred to as "another resin”). Moreover, it can also be set as the aspect containing specific resin and other resin.
- Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
- a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
- a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
- the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
- the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and 10% by mass or more. Even more preferred.
- the content of the other resin in the resin composition according to the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. and more preferably 50% by mass or more.
- the content of the resin in the resin composition according to the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the resin composition. It is more preferably 97% by mass or less, even more preferably 95% by mass or less.
- the content of the other resin is preferably 80% by mass or less with respect to the total solid content of the resin composition, and 75% by mass. It is more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 50% by mass or less, 40% by mass or less, and further can also be 30% by mass or less.
- the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
- the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
- the resin composition according to the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
- the resin composition according to the present invention preferably contains at least one resin selected from the group consisting of specific resins, phenolic resins, and epoxy resins.
- the phenolic resin may be either resole type or novolak type, and specific examples include cresol novolac resin, catechol novolak resin, resorcinol novolak resin, hydroquinone novolak resin, catechol resorcinol novolac resin, resorcinol hydroquinone novolac resin, and the like.
- Epoxy resins are not particularly limited, but are novolac type epoxy resins, bisphenol type epoxy resins, glycidylamine type epoxy resins, glycidyl ether type epoxy resins, triphenolmethane type epoxy resins, triphenolpropane type epoxy resins, alkyl-modified triphenols.
- methane-type epoxy resin triazine-nucleus-containing epoxy resin, dicyclopentadiene-modified phenol-type epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, phenol-aralkyl-type epoxy resin having at least one of a phenylene skeleton and a biphenylene skeleton, a phenylene skeleton and Examples include aralkyl epoxy resins such as naphthol aralkyl epoxy resins having at least one biphenylene skeleton, and aliphatic epoxy resins.
- the resin composition according to the present invention preferably contains a polymerizable compound.
- Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
- the resin composition (particularly, the second resin composition) according to the present invention preferably contains a compound containing an aromatic polycyclic structure, a fluorine-containing compound, or a compound having a siloxane group. Since wiring (copper, etc.) is arranged on the second resin composition, the second resin composition itself, which is in direct contact with the wiring, preferably has properties that improve the electrical performance of the wiring. , the second resin composition having a low dielectric constant is preferred.
- the compounds contained in the second resin composition include compounds containing aromatic polycyclic structures such as fluorene skeletons and polyphenylene skeletons, 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl, Fluorine-containing compounds such as 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, or compounds with siloxane groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc., which form films themselves It preferably has a relative dielectric constant of less than 3.0, more preferably 2.8 or less, even more preferably 2.6 or less.
- the lower limit of the dielectric constant is not particularly limited, and may be 0 or more.
- the dielectric loss tangent of the film formed from the compound is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
- the lower limit of the dielectric loss tangent is not particularly limited as long as it is 0 or more.
- the second resin composition preferably contains a compound containing a polymerizable group and an aromatic polycyclic structure, and more preferably contains a compound having a polymerizable group and a fluorene skeleton.
- the dielectric constant of the compound is preferably smaller than the dielectric constant of the resin contained in the second resin composition.
- the difference between the dielectric constant when the film is formed from the resin and the relative dielectric constant when the film is formed from the compound is preferably 0.2 or more, and preferably 0.4 or more. is more preferred.
- the aromatic group in the polymerizable compound having an aromatic group may be monocyclic or polycyclic, preferably polycyclic, more preferably condensed ring.
- the aromatic polycyclic structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. It is not limited to this.
- the resin composition according to the present invention preferably contains a radical cross-linking agent.
- a radical cross-linking agent is a compound having a radically polymerizable group.
- the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
- Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
- the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
- the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more.
- the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
- the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
- the resin composition according to the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
- the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
- radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
- addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
- addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
- substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
- paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
- the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
- examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc.
- polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
- JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
- JP-B-46-043946 JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493.
- vinyl phosphonic acid compounds and the like can also be mentioned.
- Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used.
- the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
- dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
- radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.
- radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
- compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
- the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
- a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
- Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
- radical cross-linking agents having an aromatic polycyclic structure include 1,3-divinylnaphthalene, acenaphthylene, 9,9-bis[4-[2-(acryloyloxy)ethoxy]phenyl]-9H-fluorene, 9, 9-bis[4-[2-[2-(acryloyloxy)ethoxy]ethoxy]phenyl]-9H-fluorene, compounds having the following structures, and the like.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
- the resin composition preferably uses a bifunctional methacrylate or acrylate.
- Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
- PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
- a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
- Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
- allyl glycidyl ether are preferably used.
- the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
- a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition according to the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
- a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
- the resin composition according to the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
- the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
- the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
- compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
- cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned.
- the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
- a melamine-based crosslinking agent is a melamine-based crosslinking agent
- a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
- an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
- a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the resin composition according to the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of cross-linking agents.
- an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
- the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
- the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
- the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
- R 100 represents an alkyl group or an acyl group.
- R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
- Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
- X represents a single bond or a divalent organic group
- each R 104 independently represents an alkyl group or an acyl group
- R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
- R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
- R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
- R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
- R 36 and R 37 may combine with each other to form a ring.
- alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- the above alkyl group may be linear or branched.
- a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
- the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
- the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
- an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
- the aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
- R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
- compounds having an alkoxymethyl group include the following structures.
- Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
- Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
- the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
- melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
- urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
- Uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
- benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
- the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
- suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
- the resin composition according to the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
- Epoxy compound (compound having an epoxy group) -
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the resin composition according to the present invention.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
- alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
- polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
- epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
- Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
- n is an integer of 1-5 and m is an integer of 1-20.
- n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
- the resin composition (particularly, the second resin composition) according to the present invention also preferably contains a polymerizable compound having an aromatic polycyclic structure as a polymerizable compound.
- a polymerizable compound having an aromatic polycyclic structure examples include compounds having the following structures.
- oxetane compound compound having an oxetanyl group
- the oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
- Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
- OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
- a benzoxazine compound (compound having a benzoxazolyl group)-
- a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
- benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
- the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition according to the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
- the resin composition according to the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat.
- a photopolymerization initiator is preferably a photoradical polymerization initiator.
- the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators.
- a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
- the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
- the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
- any known compound can be used as the photoradical polymerization initiator.
- halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
- ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
- Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
- ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
- ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
- the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.
- Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
- metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
- the photoradical polymerization initiator is more preferably an oxime compound.
- an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
- Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
- oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
- an oxime compound (oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator.
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- SpeedCure PDO manufactured by SARTOMER ARKEMA
- an oxime compound having the following structure can be used.
- An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
- oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
- An oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
- the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
- An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
- Specific examples include OE-01 to OE-75 described in WO 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
- an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
- the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
- a benzoyl group may have a substituent.
- substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
- a sulfanyl group or an amino group is more preferred.
- the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
- R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
- R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
- R X12 is an electron-withdrawing group
- R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
- oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
- oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
- photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
- More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
- At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
- the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
- benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
- 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkylbenzoin
- benzyl derivatives such as benzyl dimethyl ketal
- a compound represented by the following formula (I) can also be used.
- R 100 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); It is the same group as R 100 , and each of R 102 to R 104 is independently an alkyl group having 1 to 12 carbon atoms
- R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
- radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
- a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
- Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition according to the present invention. Yes, more preferably 0.5 to 15% by mass, still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
- the resin composition may contain a sensitizer.
- a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
- Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
- Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
- the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass.
- the sensitizers may be used singly or in combination of two or more.
- the resin composition according to the present invention may contain a chain transfer agent.
- the chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
- Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
- Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- thiol compounds can be preferably used.
- chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition according to the present invention. 0.1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
- One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
- the resin composition according to the present invention preferably also contains a thermal polymerization initiator.
- a thermal polymerization initiator in the second resin composition, for example, in the above second preheating step or the above second postheating step, the polymerization of the polymerizable compound can be promoted. can be done.
- the thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred.
- a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound.
- the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
- thermal polymerization initiators include known azo compounds and known peroxide compounds.
- azo-based compounds include azobis-based compounds.
- the azo compound may be a compound having a cyano group or a compound having no cyano group.
- Peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like.
- thermal polymerization initiator commercially available products can also be used, such as V-40, V-601 and VF-096 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Perhexyl O manufactured by NOF Corporation, Per Hexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percmyl D, Percmyl D-40, Percmyl D-40MB, Percmyl H, Percmyl P, Percmyl ND and the like.
- specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
- the content of the thermal polymerization initiator in the resin composition is preferably 0.05% by mass or more and 10% by mass or less with respect to the total solid content of the second resin composition. , more preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.
- the resin composition (particularly, the second resin composition) may contain one type of thermal polymerization initiator alone, or two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
- the resin composition according to the present invention preferably contains a photoacid generator.
- a photoacid generator is a compound that generates at least one of Bronsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm.
- the light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm.
- the photoacid generator is preferably a photoacid generator capable of generating an acid upon exposure.
- generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
- Examples of the photoacid generator used in the resin composition according to the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
- Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
- quinonediazide compounds include monovalent or polyvalent hydroxy compounds in which quinonediazide sulfonic acids are ester-bonded, monovalent or polyvalent amino compounds in which quinonediazide sulfonic acids are bonded via sulfonamides, and polyhydroxypolyamino compounds. Examples thereof include quinonediazide sulfonic acids bound by ester bonds and/or sulfonamides. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. .
- hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML
- amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
- polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited to these. .
- the quinonediazide compound preferably contains a phenol compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
- the content of the quinonediazide compound used in the resin composition according to the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin.
- a sensitizer or the like may be added as necessary.
- the photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
- the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
- X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3's, they may be the same or different.
- the alkyl group and alkoxy group in X3 above may have a substituent.
- the alkyl group for X 3 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group for X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- halogen atom for X3 a chlorine atom or a fluorine atom is preferable.
- m3 represents an integer of 0 to 3, preferably 0 or 1.
- R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxy group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
- W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
- m3 is 3
- X 3 is a methyl group
- the substitution position of X 3 is the ortho position
- R 34 is a linear alkyl group having 1 to 10 carbon atoms
- Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.
- oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674.
- the following compounds are exemplified, the contents of which are incorporated herein.
- R s1 represents an alkyl group, an aryl group or a heteroaryl group
- each R s2 which may be present in plurality, is independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom
- each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- Xs represents O or S.
- ns represents 1 or 2
- ms represents an integer of 0-6.
- an alkyl group preferably having 1 to 30 carbon atoms
- an aryl group preferably having 6 to 30 carbon atoms
- a heteroaryl group preferably having 6 to 30 carbon atoms represented by R s1 Numbers 4 to 30 are preferable
- R s1 Numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
- R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group.
- R s2 that may be present in the compound at least two times, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom.
- one is an alkyl group and the rest are hydrogen atoms.
- the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
- Xs represents O or S, preferably O.
- the ring containing Xs as a ring member is a 5- or 6-membered ring.
- ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
- an alkyl group (preferably having 1 to 30 carbon atoms) and an alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
- the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS -108) or a compound represented by the formula (OS-109).
- R t1 represents an alkyl group, an aryl group or a heteroaryl group
- R t7 represents a hydrogen atom or a bromine atom
- R t8 represents a hydrogen atom, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
- t2 represents a hydrogen atom or a methyl group.
- R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
- R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group. or represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
- R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
- Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
- oximesulfonate compound containing at least one oximesulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group.
- An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
- R u2a represents an alkyl group or an aryl group.
- Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
- R u1 to R u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , arylcarbonyl group, amido group, sulfo group, cyano group or aryl group.
- Two of R u1 to R u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
- R u1 to R u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.
- the compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
- the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
- Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
- the following b-9, b-16, b-31 and b-33 are preferred.
- Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.
- organic halogenated compounds include those described by Wakabayashi et al., "Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 , JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P. P. Hutt "Journal of Heterocyclic Chemistry” 1 (No 3), (1970), the contents of which are incorporated herein.
- Particularly preferred examples include an oxazole compound substituted with a trihalomethyl group: an S-triazine compound. More preferably, s-triazine derivatives having at least one mono-, di-, or trihalogen-substituted methyl group attached to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)- s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-( ⁇ , ⁇ , ⁇ -trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-
- organic borate compounds include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Publications, JP-A-2000-131837, JP-A-2002-107916, JP-A-2764769, JP-A-2002-116539, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, Chicago", etc., organic boron sulfonium complexes or organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561.
- JP-A-6-175554 organic boron-iodonium complexes described in JP-A-6-175553, organic boron-phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-H9 No. 7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014 and the like organoboron transition metal coordination complexes are mentioned as specific examples. incorporated herein.
- disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.
- onium salt compound for example, S.I. I. Schlesinger, Photograph. Sci. Eng. , 18, 387 (1974); S. Bal et al, Polymer, 21,423 (1980), diazonium salts, US Pat. , 055, 4,069,056, EP 104,143, US Pat. 2-150848, iodonium salts described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 German Patent Nos.
- Onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III).
- Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. ⁇ 12 alkenyl groups, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, and 1 to 12 carbon atoms.
- an alkylamino group having 2 to 12 carbon atoms a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms.
- Z 11 - represents a monovalent anion such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and a stable Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferred from the aspect.
- Ar 21 and Ar 22 each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents are 1 to 12 carbon atoms.
- an alkyl group having 2 to 12 carbon atoms an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen an atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, an alkylamido group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, carbonyl group, carboxy group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms.
- Z21 ⁇ represents a monovalent anion, and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction Perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred from the viewpoint of their properties.
- R 31 , R 32 and R 33 each independently represents an aryl group, an alkyl group, an alkenyl group or an alkynyl group having 6 to 20 carbon atoms which may have 1 to 6 substituents. In view of reactivity and stability, it is preferably an aryl group.
- Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in each alkyl group, and an alkyl group having 1 to 12 carbon atoms; 1 to 12 alkylamide or arylamido groups, carbonyl groups, carboxy groups, cyano groups, sulfonyl groups, C1 to C12 thioalkyl groups, and C1 to C12 thioaryl groups.
- Z 31 ⁇ represents a monovalent anion and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.
- Rf represents a perfluoroalkyl group.
- the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
- a photo-acid generator may be used individually by 1 type, or may be used in combination of multiple types. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
- the resin composition according to the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by physical or chemical action.
- Preferred base generators for the resin composition according to the present invention include thermal base generators and photobase generators.
- the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
- the base generator may be an ionic base generator or a non-ionic base generator.
- Examples of the base generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
- nonionic base generator examples include compounds represented by formula (B1), formula (B2), or formula (B3).
- Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
- the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
- Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
- the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
- the monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
- the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
- Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have a substituent as long as the effects of the present invention are exhibited.
- Rb 1 and Rb 2 may combine with each other to form a ring.
- the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
- Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
- Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
- an aryl group preferably
- Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
- the compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
- Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
- Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
- Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
- an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
- an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
- Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
- the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
- Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
- Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
- an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
- an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
- L is a divalent hydrocarbon group having a saturated hydrocarbon group on a linking chain path connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the linking chain path is represents a hydrocarbon group of 3 or more.
- RN1 and RN2 each independently represent a monovalent organic group.
- the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
- L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
- the linking chain is composed of four carbon atoms, and on the route of the linking chain
- the number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length”) is 4.
- the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
- the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
- the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
- the linking chain length of L is preferably 4 or 5, most preferably 4.
- Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
- the base generator preferably contains a compound represented by the following formula (N1).
- R N1 and R N2 each independently represent a monovalent organic group
- R C1 represents a hydrogen atom or a protecting group
- L represents a divalent linking group
- L is a divalent linking group, preferably a divalent organic group.
- the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
- the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
- the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
- R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 are more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
- a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
- a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
- an aliphatic hydrocarbon group preferably 1 to
- an aliphatic hydrocarbon group as R N1 and R N2 because the generated base is highly basic.
- the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
- an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
- Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
- Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
- Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
- Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
- Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
- the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
- R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
- a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
- RN1 and RN2 may be linked to each other to form a ring structure.
- the chain may have an oxygen atom or the like.
- the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
- the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
- N1 nitrogen atom in formula (N1)
- R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
- the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
- protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
- Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
- the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
- Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
- the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
- the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
- the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
- the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
- linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
- a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group and an arylenealkylene group are preferred.
- the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
- An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
- the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
- the linear or branched chain alkenylene group preferably has 1 to 10 C ⁇ C bonds, more preferably 1 to 6, even more preferably 1 to 3.
- the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
- the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
- a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
- base generators include the following, but the present invention should not be construed as being limited thereto.
- the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
- the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
- Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
- ammonium salts include the following compounds, but the present invention is not limited thereto.
- iminium salts include the following compounds, but the present invention is not limited thereto.
- the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition according to the present invention.
- the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
- the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
- One or two or more base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.
- the resin composition according to the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
- the solvent is preferably an organic solvent.
- Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
- Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
- 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
- ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
- Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
- Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
- Suitable sulfoxides include, for example, dimethyl sulfoxide.
- Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
- Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
- a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
- the content of the solvent is preferably an amount such that the total solid content concentration of the resin composition according to the present invention is 5 to 80% by mass, and the amount is 5 to 75% by mass. is more preferable, the amount of 10 to 70% by mass is more preferable, and the amount of 20 to 70% by mass is even more preferable.
- the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
- the resin composition according to the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
- the resin composition according to the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
- metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
- silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
- Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
- silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
- xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
- Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
- the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
- One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
- the resin composition according to the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
- Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
- heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
- triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
- an ion trapping agent that traps anions such as halogen ions can be used.
- Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
- the compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
- migration inhibitors include the following compounds.
- the content of the migration inhibitor is 0.01 to 5.0% by mass with respect to the total solid content of the resin composition according to the present invention. is preferred, 0.05 to 2.0 mass % is more preferred, and 0.1 to 1.0 mass % is even more preferred.
- migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
- the resin composition according to the present invention preferably contains a polymerization inhibitor.
- Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
- Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and p-tert-butylcatechol.
- the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition according to the present invention. , more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
- polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
- the resin composition according to the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
- the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa.
- the acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
- acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably.
- the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
- acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
- Acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4 ,0]undecar-7-ene and the like.
- Acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris ( t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like.
- acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
- Acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline.
- acid scavengers having a pyridine structure include pyridine and 4-methylpyridine.
- alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine and the like.
- aniline derivatives having hydroxyl groups and/or ether bonds include N,N-bis(hydroxyethyl)aniline.
- preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexyl
- compositions according to the present invention may or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually from 0.001 to 0.001 based on the total solid content of the composition. 10% by mass, preferably 0.01 to 5% by mass.
- the acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
- the resin composition of the present invention may optionally contain various additives such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, oxide Inhibitors, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.), etc., can be added. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
- surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
- the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
- the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
- a surfactant in the resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
- the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved.
- the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
- fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass Co., Ltd.
- Fluorinated surfactants compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein.
- a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
- the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
- a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
- Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
- the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
- a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
- silicone-based surfactants examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd.
- TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 manufactured by Momentive Performance Materials
- KP341, KF6001, KF6002 manufactured by Shin-Etsu Silicone Co., Ltd.
- BYK307, BYK323, and BYK330 manufactured by BYK-Chemie Co., Ltd.
- Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
- cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
- anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
- the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
- a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. It may be unevenly distributed on the surface of the composition.
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition according to the present invention. . Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
- the resin composition according to the present invention may contain inorganic particles.
- inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
- the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
- the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
- the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
- salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like.
- benzophenone-based UV absorbers examples include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone.
- benzotriazole-based UV absorbers examples include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,
- Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
- examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(
- the above various ultraviolet absorbers may be used singly or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
- the resin composition of this embodiment may contain an organic titanium compound.
- an organic titanium compound By containing the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
- Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
- titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
- Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
- Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
- Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
- Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
- the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
- titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
- the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
- the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
- compositions of the present invention may contain antioxidants.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
- Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
- the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
- Phosphorus-based antioxidants can also be suitably used as antioxidants.
- a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
- antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
- compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
- the composition of the present invention may also contain latent antioxidants, if desired.
- the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
- a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
- latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein.
- Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
- Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group.
- R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom.
- k represents an integer of 1 to 4;
- the compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
- R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, - O--, --NH--, --NHNH--, combinations thereof, and the like, which may further have a substituent.
- Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
- the amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
- Anti-aggregation agents include sodium polyacrylate and the like.
- the aggregation inhibitor may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
- the resin composition of the present embodiment may contain a phenolic compound as necessary.
- phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
- one type of phenolic compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
- Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
- Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
- composition of the present invention may or may not contain other polymer compounds, but if it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
- the viscosity of the resin composition according to the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
- the water content of the resin composition according to the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
- the metal content of the resin composition according to the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
- a raw material having a low metal content is selected as a raw material constituting the resin composition according to the present invention.
- Examples include a method such as performing filter filtration on the raw material constituting the resin composition, or performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like. .
- the resin composition according to the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, more preferably less than 300 ppm by mass, and 200 ppm by mass from the viewpoint of wiring corrosion resistance. Less than is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
- Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known container can be used as the container for the resin composition of the present invention.
- the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
- a precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
- the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer.
- the resulting crude polymer was collected by filtration and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution.
- the resulting crude polymer solution was dropped into 3 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer P-2.
- the weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
- Polymer P-2 is a resin having the following structure. Subscripts in parentheses represent the molar ratio of each repeating unit.
- composition was obtained by mixing the components shown in the table below. Specifically, the contents of the components described in the table were the amounts (parts by mass) described in the table. In the table, the description of "-" indicates that the composition does not contain the corresponding component.
- ⁇ D-1 KBM-403 (3-glycidoxypropyltrimethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.)
- ⁇ D-2 ⁇ -ureidopropyltriethylsilane
- ⁇ D-3 N-[3-(triethoxysilyl)propyl]maleamic acid
- ⁇ D-4 N-(3-triethoxysilyl)propyl)-phthalamic acid
- ⁇ D-5 KBM-502 (3-methacryloxypropylmethyldimethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.)
- F-1 2MeHQ (methoxyhydroquinone)
- F-2 TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dixoid)
- F-3 4MeHQ (4-methoxyphenol)
- F-4 PBQ (p-benzoquinone)
- I-1 compound having the following structure • I-2: compound having the following structure, Et represents an ethyl group. ⁇ I-3: N-phenyldiethanolamine ⁇ I-4: A compound having the following structure ⁇ I-5: TrisP-PA ( ⁇ , ⁇ , ⁇ '-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene )
- Example 1 After spin coating, the first composition was heated under the conditions shown in the table as treatment 1 (treatment 1) to form a coating film having the thickness shown in the table. As treatment 2, composition 8 was applied on the coating film obtained thereafter to form a coating film of 5 ⁇ m. As processing 3, an i-line exposure machine was used to expose a recessed pattern (extraction) through a mask. As processing 4, development was performed for 60 seconds with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution. Dry etching was performed using the pattern of composition 8 obtained as treatment 5 as a mask to obtain a pattern of the first composition. A second composition was further applied over the pattern of the first composition formed through the previous step. After performing the processing 1 of the second composition, the development of the processing 2 was performed to obtain a composite pattern.
- treatment 1 treatment 1
- TMAH tetramethylammonium hydroxide
- Example 2 After the first composition was spin-coated, as process 1, an i-line exposure machine was used to expose a recessed pattern (extraction) through a mask. As processing 2, development was performed for 60 seconds with a 2.38% by mass TMAH aqueous solution. As treatment 3, post-heating was performed under the conditions shown in the table to obtain a pattern of the first composition. A second composition was further applied over the pattern of the first composition formed through the previous step. After performing the processing 1 of the second composition, the development of the processing 2 was performed to obtain a composite pattern.
- Example 3 After the first composition was spin-coated, as treatment 1, an i-line exposure machine was used to expose a recessed pattern (outlet) through a mask. As processing 2, development was performed with PGMEA (propylene glycol monomethyl ether acetate) for 60 seconds. Post-heating was performed as treatment 3 to obtain a pattern of the first composition. A second composition was further applied over the pattern of the first composition formed through the previous step. After performing the processing 1 of the second composition, the development of the processing 2 was performed to obtain a composite pattern.
- PGMEA propylene glycol monomethyl ether acetate
- Example 4-17> After the first composition was spin-coated, as treatment 1, an i-line exposure machine was used to expose a recessed pattern (outlet) through a mask. As processing 2, development was performed with cyclopentanone for 60 seconds. Post-heating was performed as treatment 3 to obtain a pattern of the first composition. A second composition was further applied over the pattern of the first composition formed through the previous step. After the treatment 1 of the second composition was carried out, the development of treatment 2 was carried out, and the heating of treatment 3 was carried out to obtain a composite pattern. However, in the treatment 2 of the second composition of Example 11, the treatment described in Example 3 was performed.
- the top pattern width of the pattern of the first composition was measured using a cross-sectional SEM (cross-sectional observation with a scanning electron microscope).
- the pattern width was set to D1.
- the pattern width of the composite pattern after all the treatments of the second composition is D2, the case where D2-D1 is 0.5 ⁇ m or more is “determination A”, and the case where it is 0.2 ⁇ m or more and less than 0.5 ⁇ m is “ A case of less than 0.2 ⁇ m was judged to be “judgment B”, and a case of less than 0.2 ⁇ m was judged to be “judgment C”.
- the evaluation results are shown in the "shrink evaluation" column of the table below. It can be said that the larger D2 ⁇ D1 is, the finer the pattern can be formed.
- a composite pattern was applied to the copper pattern in the same manner as in Examples 1 to 17 above, except that the silicon wafer was changed to a substrate having a 10 ⁇ m LS (line and space) copper pattern.
- the substrate was placed in an oven at 175°C and held for 500 hours. After that, the substrate was taken out from the oven, cross-sectionally cut using an ion milling device, and cross-sectionally observed with a SEM (scanning electron microscope).
- a composite pattern was formed on the copper oxide film in the same manner as in Examples 1 to 17 above, except that the silicon wafer was changed to an 8-inch wafer having a copper oxide film. At the time of i-line exposure, a photomask capable of forming a pattern of 30 ⁇ 40 mm was used. After all the treatments described in the above table for the second composition are completed, the wafer is slowly cooled and then immersed in 2N (2 mol/L)-hydrochloric acid for 2 hours to peel off the film of the resin composition from the wafer. , and after washing with water, 30 x 4 mm strip-shaped membranes of the composite patterns of Examples 1-17 were obtained.
- the dielectric constants shown in the above table were obtained by forming a single film and measuring under the condition 1 above.
- fine patterns can be formed according to the method for producing a permanent film of the present invention.
Abstract
Description
例えば、特許文献1には、水酸基を含有する樹脂と、架橋成分と、アルコール溶媒とを含有する微細パターン形成用樹脂組成物であって、架橋成分として特定の構造を有する化合物を含む微細パターン形成用樹脂組成物が記載されている。
特許文献2には、(A)ビニルピロリドンと、(B)(A)成分以外の水溶性ビニル化合物の中から選ばれた少なくとも1種のモノマーとの共重合体を含む水溶液からなるレジストパターン微細化用被覆形成剤が記載されている。 2. Description of the Related Art In recent years, with the miniaturization of semiconductor elements and the like, various methods of forming fine patterns by lithography or the like have been studied in the manufacture of semiconductor elements.
For example,
本発明は、微細な永久膜のパターンを形成することができる永久膜の製造方法、上記永久膜の製造方法を含む積層体の製造方法、及び、上記永久膜の製造方法又は上記積層体の製造方法を含む半導体デバイスの製造方法を提供することを目的とする。 When a resin composition is used to form a patterned permanent film included in a device such as a semiconductor element, for example, there is a demand for miniaturization of the shape of the resulting pattern (for example, formation of a fine via pattern). be.
The present invention provides a method for producing a permanent film capable of forming a fine pattern of the permanent film, a method for producing a laminate including the method for producing the permanent film, and a method for producing the permanent film or production of the laminate. It is an object of the present invention to provide a method of manufacturing a semiconductor device, including a method.
<1> 第1の樹脂組成物を用いて、第1の樹脂組成物膜を基材上に形成し、第1のパターンを有する基材を得る工程、
上記第1のパターンを有する基材上に、第2の樹脂組成物を付与し、第1のパターン上、及び、第1のパターンの間の領域に第2の樹脂組成物の被膜を形成する工程、及び、
第2の樹脂組成物の被膜の一部を除去し、第1のパターンと接する第2のパターンを形成する工程を含み、
上記第1のパターンにおけるパターンの間の領域よりも、上記第1のパターン及び上記第2のパターンからなる複合パターンにおけるパターンの間の領域の方が狭い、
永久膜の製造方法。
<2> 上記第1の樹脂組成物がネガ型感放射線性樹脂組成物である、<1>に記載の硬化膜の製造方法。
<3> 上記第1のパターンを有する基材を得る工程が、上記第1の樹脂組成物膜を選択的に露光した後に、溶剤現像により現像する工程である、<1>又は<2>に記載の永久膜の製造方法。
<4> 上記第2のパターンを形成する工程が、上記第2の樹脂組成物の被膜の一部を溶剤現像により除去する工程である、<1>~<3>のいずれか1つに記載の永久膜の製造方法。
<5> 上記第2の樹脂組成物の被膜を形成する工程の後、上記第2のパターンを形成する工程の前に、上記第1のパターン及び上記第2の樹脂組成物の被膜を加熱する工程を更に含む、<1>~<4>のいずれか1つに記載の永久膜の製造方法。
<6> 上記第2の樹脂組成物が、熱重合開始剤を含む、<1>~<5>のいずれか1つに記載の永久膜の製造方法。
<7> 上記第2の樹脂組成物が、重合性基を有する樹脂を含む、<1>~<6>のいずれか1つに記載の永久膜の製造方法。
<8> 上記第2の樹脂組成物が、重合性基及びフルオレン環構造を有する化合物を含む、<1>~<7>のいずれか1つに記載の永久膜の製造方法。
<9> 上記第1の樹脂組成物に含まれる樹脂が、ポリイミド前駆体又はポリベンゾオキサゾール前駆体である、<1>~<8>のいずれか1つに記載の永久膜の製造方法。
<10> 上記第2の樹脂組成物に含まれる樹脂が、ポリイミド前駆体又はポリベンゾオキサゾール前駆体である、<1>~<9>のいずれか1つに記載の永久膜の製造方法。
<11> 得られる永久膜が、ポリイミド又はポリベンゾオキサゾールを含む、<1>~<10>のいずれか1つに記載の永久膜の製造方法。
<12> 上記第2のパターンを形成する工程の後に、加熱工程を更に含む、<1>~<11>のいずれか1つに記載の永久膜の製造方法。
<13> 上記複合パターンの破断伸びが、40%以上である、<1>~<12>のいずれか1つに記載の永久膜の製造方法。
<14> 上記第1のパターンが、ホールパターン及びトレンチパターンの少なくとも一方を含む、<1>~<13>のいずれか1つに記載の永久膜の製造方法。
<15> <1>~<14>のいずれか1つに記載の永久膜の製造方法を含む、積層体の製造方法。
<16> <1>~<14>のいずれか1つに記載の永久膜の製造方法、又は、<15>に記載の積層体の製造方法を含む、半導体デバイスの製造方法。 Examples of representative embodiments of the present invention are provided below.
<1> A step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern;
A second resin composition is applied onto the substrate having the first pattern, and a coating of the second resin composition is formed on the first pattern and on the region between the first patterns. process, and
removing a portion of the coating of the second resin composition to form a second pattern in contact with the first pattern;
The area between the patterns in the composite pattern consisting of the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.
A method for manufacturing a permanent membrane.
<2> The method for producing a cured film according to <1>, wherein the first resin composition is a negative radiation-sensitive resin composition.
<3><1> or <2>, wherein the step of obtaining the base material having the first pattern is a step of selectively exposing the first resin composition film and then developing by solvent development; A method of making the described permanent film.
<4> Any one of <1> to <3>, wherein the step of forming the second pattern is a step of removing part of the film of the second resin composition by solvent development. method for producing a permanent film of
<5> After the step of forming the coating of the second resin composition and before the step of forming the second pattern, the first pattern and the coating of the second resin composition are heated. The method for producing a permanent film according to any one of <1> to <4>, further comprising a step.
<6> The method for producing a permanent film according to any one of <1> to <5>, wherein the second resin composition contains a thermal polymerization initiator.
<7> The method for producing a permanent film according to any one of <1> to <6>, wherein the second resin composition contains a resin having a polymerizable group.
<8> The method for producing a permanent film according to any one of <1> to <7>, wherein the second resin composition contains a compound having a polymerizable group and a fluorene ring structure.
<9> The method for producing a permanent film according to any one of <1> to <8>, wherein the resin contained in the first resin composition is a polyimide precursor or a polybenzoxazole precursor.
<10> The method for producing a permanent film according to any one of <1> to <9>, wherein the resin contained in the second resin composition is a polyimide precursor or a polybenzoxazole precursor.
<11> The method for producing a permanent film according to any one of <1> to <10>, wherein the obtained permanent film contains polyimide or polybenzoxazole.
<12> The method for producing a permanent film according to any one of <1> to <11>, further including a heating step after the step of forming the second pattern.
<13> The method for producing a permanent film according to any one of <1> to <12>, wherein the composite pattern has an elongation at break of 40% or more.
<14> The method for producing a permanent film according to any one of <1> to <13>, wherein the first pattern includes at least one of a hole pattern and a trench pattern.
<15> A method for producing a laminate, including the method for producing a permanent film according to any one of <1> to <14>.
<16> A method for manufacturing a semiconductor device, including the method for manufacturing a permanent film according to any one of <1> to <14> or the method for manufacturing a laminate according to <15>.
本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC)法を用いて測定した値であり、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、及び、TSKgel Super HZ2000(以上、東ソー(株)製)を直列に連結して用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。ただし、溶解性が低い場合など、溶離液としてTHFが適していない場合にはNMP(N-メチル-2-ピロリドン)を用いることもできる。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、樹脂組成物層がある場合には、基材から樹脂組成物層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
As used herein, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Moreover, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values. In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, unless otherwise specified, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". and the opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH unless otherwise specified.
Combinations of preferred aspects are more preferred aspects herein.
本発明の永久膜の製造方法は、第1の樹脂組成物を用いて、第1の樹脂組成物膜を基材上に形成し、第1のパターンを有する基材を得る工程、上記第1のパターンを有する基材上に、第2の樹脂組成物を付与し、第1のパターン上、及び、第1のパターンの間の領域に第2の樹脂組成物の被膜を形成する工程、及び、第2の樹脂組成物の被膜の一部を除去し、第1のパターンと接する第2のパターンを形成する工程を含み、上記第1のパターンにおけるパターンの間の領域よりも、上記第1のパターン及び上記第2のパターンからなる複合パターンにおけるパターンの間の領域の方が狭い。 (Manufacturing method of permanent film)
The method for producing a permanent film of the present invention includes a step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern; A step of applying a second resin composition on a substrate having a pattern of and forming a coating of the second resin composition on the first pattern and on the area between the first patterns; , removing a portion of the coating of the second resin composition to form a second pattern in contact with the first pattern, wherein the first pattern is less than the area between the patterns in the first pattern. and the second pattern, the area between the patterns is narrower.
上記効果が得られるメカニズムは不明であるが、下記のように推測される。 According to the permanent film manufacturing method of the present invention, a fine permanent film pattern can be formed.
Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.
従来は、樹脂組成物をパターン状に露光及び現像する、又は、樹脂組成物上にレジストパターンを形成して、レジストパターンをマスクとして樹脂組成物のエッチングを行う等の方法により樹脂組成物のパターンを形成していたが、使用する材料の特性、露光に用いる露光波長の限界等により、パターンの微細化には限界があった。
本発明においては、第1のパターンを形成した後に、第1のパターン上に第2の樹脂組成物の被膜を形成し、その後第2の樹脂組成物の被膜の一部を除去し、第2のパターンを形成することにより、第1のパターンにおけるパターンの間の領域よりも、第1のパターンと第2のパターンからなる複合パターンにおけるパターンの間の領域の方が狭くなる。
ここで、パターン間の領域が狭い、すなわち、パターン間の距離が小さくなることにより、微細な永久膜のパターン(例えば、微細なホールパターン、微細なトレンチパターンなど)を製造することができる。
そのため、第1のパターンのみを形成する場合と比較して、パターン間の寸法が小さい、微細なパターンを形成することができると考えられる。
すなわち、本発明によれば、例えばホールパターン、トレンチパターンなどの限界寸法を小さくすることが可能となる。 As described above, when forming a patterned permanent film included in a device such as a semiconductor element using a resin composition, it is desired to refine the shape of the resulting pattern (for example, a fine hole pattern, or There is a demand for forming a fine trench pattern, etc.).
Conventionally, the resin composition is patterned by exposure and development, or by forming a resist pattern on the resin composition and etching the resin composition using the resist pattern as a mask. However, due to the characteristics of the materials used, the limits of the exposure wavelength used for exposure, etc., there was a limit to miniaturization of the pattern.
In the present invention, after forming the first pattern, a coating of the second resin composition is formed on the first pattern, and then a part of the coating of the second resin composition is removed to form the second pattern. , the area between the patterns in the composite pattern consisting of the first pattern and the second pattern is narrower than the area between the patterns in the first pattern.
Here, since the area between patterns is narrow, that is, the distance between patterns is small, fine permanent film patterns (for example, fine hole patterns, fine trench patterns, etc.) can be manufactured.
Therefore, it is conceivable that a fine pattern with a small dimension between patterns can be formed as compared with the case of forming only the first pattern.
That is, according to the present invention, it is possible to reduce the critical dimensions of, for example, hole patterns, trench patterns, and the like.
加えて、第1の樹脂組成物が重合性基を有する樹脂を含み、第2の樹脂組成物が重合性基を有する成分(重合性基を有する樹脂、重合性化合物など)を含むことにより、パターンの信頼性を向上することもできる。上記態様において、第1の樹脂組成物と第2の樹脂組成物として、同じ樹脂を含む樹脂組成物を用いることも、信頼性の向上に寄与すると考えられる。
ここで、パターンの信頼性とは、長期間の経過後においても基材とパターンとの間で剥離が生じにくいことをいう。 Moreover, in addition to the reduction in the dimension between the patterns, the thickness of the pattern itself can be increased as compared with the case where only the first pattern is formed. Therefore, it is also possible to increase the aspect ratio of the pattern.
In addition, the first resin composition contains a resin having a polymerizable group, and the second resin composition contains a component having a polymerizable group (a resin having a polymerizable group, a polymerizable compound, etc.), It is also possible to improve the reliability of the pattern. In the above aspect, it is considered that using resin compositions containing the same resin as the first resin composition and the second resin composition also contributes to the improvement of reliability.
Here, the reliability of the pattern means that peeling is unlikely to occur between the substrate and the pattern even after a long period of time.
図1(a)は、基材1上に第1のパターン2を有する基材の一例を示している。
図1(a)中、基材1上に第1のパターン2が形成されており、2つの第1のパターンの間にはパターン間の領域4(パターンが存在しない領域)が形成されている。
図1(b)は、第1のパターン上、及び、第1のパターンの間の領域に第2の樹脂組成物の被膜が形成された状態の一例を示している。
図1(b)中、第2の樹脂組成物の被膜6が、第1のパターン2上及びパターン間の領域4に形成されている。
図1(c)は、図1(b)に示す第2の樹脂組成物の被膜の一部を除去する際に、第2の樹脂組成物の被膜の除去される領域8を示している。図1(c)における破線の外側(第2の樹脂組成物の被膜6が第1のパターン2と接する側とは反対の側)に存在する領域が、除去される領域8である。除去方法については後述する。
図1(d)は、第2の樹脂組成物の被膜の一部が除去された状態の一例を示している。
図1(c)における上記領域8が除去され、図1(d)においては第1のパターン2及び第2のパターン10からなる複合パターンが形成されている。
図1(d)においては、便宜上、第1のパターン2と第2のパターン10を区別して記載しているが、これらは各パターンに含まれる成分の共有結合等により一体となっていてもよい。
ここで、図1(d)における複合パターンのパターン間の領域12は、図1(a)におけるパターン間の領域4よりも狭くなる。
このように、本発明の永久膜の製造方法によれば、第1のパターンのみによりパターンを形成する場合と比較して、パターン間の領域を狭くすることができる。すなわち、微細なパターンを形成することができる。
以下、本発明の永久膜の製造方法に含まれる各工程について詳細に説明する。 An example of the method for producing the permanent film of the present invention is shown in FIG.
FIG. 1(a) shows an example of a substrate having a
In FIG. 1(a), a
FIG. 1(b) shows an example of a state in which a film of the second resin composition is formed on the first pattern and on the regions between the first patterns.
In FIG. 1(b), a
FIG. 1(c) shows a
FIG. 1(d) shows an example of a state in which part of the coating of the second resin composition is removed.
The
In FIG. 1(d), for convenience, the
Here, the
As described above, according to the method for producing a permanent film of the present invention, the area between patterns can be narrowed compared to the case where the pattern is formed only by the first pattern. That is, fine patterns can be formed.
Hereinafter, each step included in the method for producing a permanent film of the present invention will be described in detail.
本発明の永久膜の製造方法は、第1の樹脂組成物を用いて、第1の樹脂組成物膜を基材上に形成し、第1のパターンを有する基材を得る工程(「第1のパターン形成工程」ともいう。)を含む。
第1の樹脂組成物の詳細については後述する。
第1のパターン形成工程は、第1の樹脂組成物を基材上に適用して膜を形成する第1の膜形成工程を含むことが好ましい。
また、第1のパターン形成工程は、上記第1の膜形成工程、第1の膜形成工程により形成された膜を選択的に露光する第1の露光工程、及び、第1の露光工程により露光された膜を現像液を用いて現像してパターンを形成する第1の現像工程を含むことがより好ましい。
中でも、第1のパターンを有する基材を得る工程は、上記第1の樹脂組成物膜を選択的に露光した後に、溶剤現像により現像する工程であることが好ましい。溶剤現像とは、現像液として後述する有機溶剤を含む現像液を用いた現像をいう。
すなわち、第1の樹脂組成物膜は、露光及び現像に供される感光膜であることが好ましく、露光及び有機溶剤を含む現像液を用いた現像に供される感光膜であることが好ましい。
また、第1の樹脂組成物膜は、ポジ型現像に供される感光膜であってもよいし、ネガ型現像に供される感光膜であってもよいが、ネガ型現像に供される感光膜であることがより好ましい。
本発明において、ネガ型現像とは、現像により非露光部が除去される現像をいい、ポジ型現像とは、現像により露光部が除去される現像をいう。
また、第1のパターン形成工程は、上記第1の膜形成工程、上記第1の露光工程、上記第1の現像工程、並びに、第1の現像工程により得られたパターンを加熱する第1の加熱工程及び現像工程により得られたパターンを露光する第1の現像後露光工程の少なくとも一方を含むことが特に好ましい。 <First pattern forming step>
The method for producing a permanent film of the present invention includes a step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern ("first Also referred to as "pattern formation step".).
The details of the first resin composition will be described later.
The first pattern forming step preferably includes a first film forming step of applying the first resin composition onto the substrate to form a film.
The first pattern forming step includes the first film forming step, a first exposure step of selectively exposing the film formed by the first film forming step, and exposure by the first exposure step. It is more preferable to include a first developing step of developing the coated film with a developer to form a pattern.
Among them, the step of obtaining the base material having the first pattern is preferably a step of selectively exposing the first resin composition film and then developing it by solvent development. Solvent development refers to development using a developer containing an organic solvent, which will be described later.
That is, the first resin composition film is preferably a photosensitive film subjected to exposure and development, and preferably a photosensitive film subjected to exposure and development using a developer containing an organic solvent.
The first resin composition film may be a photosensitive film subjected to positive development or a photosensitive film subjected to negative development. A photosensitive film is more preferable.
In the present invention, negative development refers to development in which non-exposed areas are removed, and positive development refers to development in which exposed areas are removed.
The first pattern forming step includes the first film forming step, the first exposing step, the first developing step, and a first step of heating the pattern obtained by the first developing step. It is particularly preferred to include at least one of a first post-development exposure step of exposing the pattern obtained by the heating step and the developing step.
ホールパターンとしては、例えば、直径が0.5~100μmのホールパターンが挙げられ、直径が3~50μmのホールパターンが好ましい。またホールの形状は特に限定されないが、例えば上面から見た形状が円形状であるホールパターンが挙げられる。上記円形状である場合には、上記ホールパターンの直径とは上記円の直径を、上記形状が円形状でない場合には、上記ホールパターンの直径とは、ホールパターンを上面から見た形状の円相当径(ある面積を有する形状において、その面積と同一面積である円の直径)を意味する。
トレンチパターンとしては、例えば、トレンチ幅0.5~100μmのトレンチパターンが挙げられ、トレンチ幅が3~50μmのトレンチパターンが好ましい。
第1のパターンの膜厚としては、1~50μmであることが好ましく、2~20μmであることがより好ましく、3~15μmであることが更に好ましい。 Also, the first pattern preferably includes at least one of a hole pattern (eg, via pattern) and a trench pattern.
As the hole pattern, for example, a hole pattern with a diameter of 0.5 to 100 μm can be mentioned, and a hole pattern with a diameter of 3 to 50 μm is preferable. Although the shape of the holes is not particularly limited, for example, a hole pattern having a circular shape when viewed from above can be used. When the shape is circular, the diameter of the hole pattern is the diameter of the circle, and when the shape is not circular, the diameter of the hole pattern is the circle of the shape of the hole pattern when viewed from above. It means an equivalent diameter (in a shape with a certain area, the diameter of a circle that has the same area as that area).
As the trench pattern, for example, a trench pattern with a trench width of 0.5 to 100 μm can be mentioned, and a trench pattern with a trench width of 3 to 50 μm is preferable.
The film thickness of the first pattern is preferably 1 to 50 μm, more preferably 2 to 20 μm, even more preferably 3 to 15 μm.
本発明の永久膜の製造方法は、第1の樹脂組成物を基材上に適用して膜を形成する第1の膜形成工程を含むことが好ましい。 [First film forming step]
The method for producing a permanent film of the present invention preferably includes a first film forming step of applying the first resin composition onto a substrate to form a film.
基材の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基材、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基材(例えば、金属から形成された基材、及び、金属層が例えばめっきや蒸着等により形成された基材のいずれであってもよい)、紙、SOG(Spin On Glass)、TFT(薄膜トランジスタ)アレイ基材、モールド基材、プラズマディスプレイパネル(PDP)の電極板などが挙げられ、特に制約されない。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Cu基材およびモールド基材がより好ましい。
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材の形状は特に限定されず、円形状であってもよく、矩形状であってもよい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。
また、基材としては、例えば板状、好ましくはパネル状の基材(基板)が用いられる。 -Base material-
The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
In addition, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
Moreover, the shape of the substrate is not particularly limited, and may be circular or rectangular.
As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. In the case of a rectangular shape, the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
As the base material, for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、バックリンスなどが挙げられる。
また第1の樹脂組成物を基材に塗布する前に基材に種々の溶剤を塗布し、基材の濡れ性を向上させた後に第1の樹脂組成物を塗布するプリウェット工程を採用してもよい。 Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the first resin composition according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, ink jet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
Also, a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
In addition, a pre-wetting step is employed in which various solvents are applied to the base material before applying the first resin composition to the base material to improve the wettability of the base material, and then the first resin composition is applied. may
上記膜は、第1の膜形成工程(層形成工程)の後に(第1の樹脂組成物を基材上に適用した後に)、溶剤を除去するために形成された膜(層)を乾燥する工程(第1の乾燥工程)に供されてもよい。
すなわち、第1のパターン形成工程は、第1の膜形成工程により形成された膜を乾燥する第1の乾燥工程を含んでもよい。
また、上記第1の乾燥工程は第1の膜形成工程の後、第1の露光工程の前に行われることが好ましい。
第1の乾燥工程における膜の乾燥温度は50~150℃であることが好ましく、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。また、減圧により乾燥を行っても良い。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、2分~7分がより好ましい。 [First drying step]
After the first film forming step (layer forming step) (after applying the first resin composition onto the substrate), the film (layer) formed is dried to remove the solvent. It may be subjected to a step (first drying step).
That is, the first pattern forming step may include a first drying step of drying the film formed by the first film forming step.
Also, the first drying step is preferably performed after the first film forming step and before the first exposure step.
The drying temperature of the film in the first drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
本発明の永久膜の製造方法は、第1の膜形成工程により形成された膜を選択的に露光する第1の露光工程を含んでもよい。
選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域(露光部)と露光されていない領域(非露光部)が形成される。
露光量は、第1の樹脂組成物を感光できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で50~10,000mJ/cm2が好ましく、200~8,000mJ/cm2がより好ましい。 [First exposure step]
The method for producing a permanent film of the present invention may include a first exposure step of selectively exposing the film formed by the first film forming step.
Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
The amount of exposure is not particularly defined as long as it can sensitize the first resin composition. is more preferred.
また、露光の方式は特に限定されず、第1の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。 In relation to the light source, the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. be done. Among these, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
The method of exposure is not particularly limited as long as at least a part of the film made of the first resin composition is exposed. mentioned.
上記膜は、露光後に加熱する工程(第1の露光後加熱工程)に供されてもよい。
すなわち、本発明の永久膜の製造方法は、第1の露光工程により露光された膜を加熱する第1の露光後加熱工程を含んでもよい。
第1の露光後加熱工程は、第1の露光工程後、第1の現像工程前に行うことができる。
第1の露光後加熱工程における加熱温度は、50℃~140℃であることが好ましく、60℃~120℃であることがより好ましい。
第1の露光後加熱工程における加熱時間は、30秒間~300分間が好ましく、1分間~10分間がより好ましい。
第1の露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで1~12℃/分が好ましく、2~10℃/分がより好ましく、3~10℃/分が更に好ましい。
また、昇温速度は加熱途中で適宜変更してもよい。
第1の露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。 [First post-exposure heating step]
The film may be subjected to a step of heating after exposure (first post-exposure heating step).
That is, the method for producing a permanent film of the present invention may include a first post-exposure heating step of heating the film exposed by the first exposure step.
The first post-exposure heating step can be performed after the first exposure step and before the first development step.
The heating temperature in the first post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
The heating time in the first post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the first post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and further preferably 3 to 10° C./min from the temperature at the start of heating to the maximum heating temperature. preferable.
Also, the rate of temperature increase may be appropriately changed during heating.
The heating means in the first post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used.
It is also preferable to perform the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
露光後の上記膜は、現像液を用いて現像してパターンを形成する第1の現像工程に供されてもよい。
すなわち、本発明の永久膜の製造方法は、第1の露光工程により露光された膜を現像液を用いて現像してパターンを形成する第1の現像工程を含んでもよい。現像を行うことにより、膜の露光部及び非露光部のうち一方が除去され、パターンが形成される。
ここで、膜の非露光部が現像工程により除去される現像をネガ型現像といい、膜の露光部が現像工程により除去される現像をポジ型現像という。 [First development step]
The film after exposure may be subjected to a first development step in which the film is developed using a developer to form a pattern.
That is, the method for producing a permanent film of the present invention may include a first development step of developing the film exposed in the first exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
Here, development in which the unexposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.
第1の現像工程において用いられる現像液としては、アルカリ水溶液、又は、有機溶剤を含む現像液が挙げられる。 -developer-
Examples of the developer used in the first development step include a developer containing an alkaline aqueous solution or an organic solvent.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、膜が形成された基材を現像液に浸漬する方法、基材上に形成された膜にノズルを用いて現像液を供給するパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 -Method of supplying developer-
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle. There is a method of puddle development or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer with a straight nozzle, the substrate is spun to remove the developer from the substrate. A step of removing from above may be employed, and this step may be repeated multiple times.
The method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material. A process of vibrating with sound waves or the like and a process of combining them can be employed.
現像液がアルカリ水溶液である場合、リンス液としては、例えば水を用いることができる。現像液が有機溶剤を含む現像液である場合、リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤(例えば、水、現像液に含まれる有機溶剤とは異なる有機溶剤)を用いることができる。 -Rinse liquid-
When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドルによる供給、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記現像後のパターンに対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 - Rinse liquid supply method -
The method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed. There is a method of continuously supplying the rinsing liquid onto the material using means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
That is, the rinsing step is preferably a step of supplying the rinse liquid to the pattern after the development through a straight nozzle or a step of continuously supplying the rinse liquid, and more preferably a step of supplying the rinse liquid through a spray nozzle.
The method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be employed.
第1の現像工程により得られたパターン(リンス工程を行う場合は、リンス後のパターン)は、上記現像により得られたパターンを加熱する第1の加熱工程に供されてもよい。
すなわち、本発明の永久膜の製造方法は、第1の現像工程により得られたパターンを加熱する第1の加熱工程を含んでもよい。
また、本発明の永久膜の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、第1の膜形成工程により得られた膜を加熱する第1の加熱工程を含んでもよい。
第1の加熱工程における加熱温度(最高加熱温度)としては、50~200℃が好ましく、60~160℃がより好ましく、70~150℃が更に好ましく、80~140℃が一層好ましく、90~120℃が特に好ましい。 [First heating step]
The pattern obtained by the first developing step (the pattern after rinsing when the rinsing step is performed) may be subjected to the first heating step of heating the pattern obtained by the above developing.
That is, the method for producing a permanent film of the present invention may include a first heating step of heating the pattern obtained by the first developing step.
In addition, the method for producing a permanent film of the present invention includes a first heating step of heating the pattern obtained by another method without performing the developing step or the film obtained by the first film forming step. It's okay.
The heating temperature (maximum heating temperature) in the first heating step is preferably 50 to 200°C, more preferably 60 to 160°C, still more preferably 70 to 150°C, even more preferably 80 to 140°C, and 90 to 120°C. °C is particularly preferred.
加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。 Heating in the first heating step is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12° C./min. The rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 °C/sec is more preferred.
第1の加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。 The first heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
The heating means in the first heating step is not particularly limited, but includes, for example, a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
第1の現像工程により得られたパターン(リンス工程を行う場合は、リンス後のパターン)は、上記第1の加熱工程に代えて、又は、上記第1の加熱工程に加えて、現像工程後のパターンを露光する第1の現像後露光工程に供されてもよい。
すなわち、本発明の永久膜の製造方法は、第1の現像工程により得られたパターンを露光する第1の現像後露光工程を含んでもよい。本発明の永久膜の製造方法は、第1の加熱工程及び第1の現像後露光工程を含んでもよいし、第1の加熱工程及び第1の現像後露光工程の一方のみを含んでもよい。
第1の現像後露光工程においては、例えば、光塩基発生剤の感光によってポリイミド前駆体等の環化が進行する反応や、光酸発生剤の感光によって酸分解性基の脱離が進行する反応などを促進することができる。
第1の現像後露光工程においては、第1の現像工程において得られたパターンの少なくとも一部が露光されればよいが、上記パターンの全部が露光されることが好ましい。
第1の現像後露光工程における露光量は、感光性化合物が感度を示す波長における露光エネルギー換算で、50~20,000mJ/cm2であることが好ましく、100~15,000mJ/cm2であることがより好ましい。
第1の現像後露光工程は、例えば、上述の第1の露光工程における光源を用いて行うことができ、ブロードバンド光を用いることが好ましい。 [First post-development exposure step]
The pattern obtained by the first developing step (pattern after rinsing when performing the rinsing step) is replaced with the first heating step or in addition to the first heating step after the developing step. may be subjected to a first post-development exposure step that exposes a pattern of .
That is, the method for producing a permanent film of the present invention may include a first post-development exposure step of exposing the pattern obtained by the first development step. The method for producing a permanent film of the present invention may include the first heating step and the first post-development exposure step, or may include only one of the first heating step and the first post-development exposure step.
In the first post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator. etc. can be promoted.
In the first post-development exposure step, at least part of the pattern obtained in the first development step may be exposed, but it is preferable to expose the entire pattern.
The exposure amount in the first post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength at which the photosensitive compound exhibits sensitivity. is more preferable.
The first post-development exposure step can be performed using, for example, the light source in the first exposure step described above, and broadband light is preferably used.
また、第1のパターン形成工程は、上記第1の膜形成工程後に、他の膜形成工程を含み、他の膜形成工程により得られた膜を露光、現像等によりパターン化した後に、上記パターンをマスクとしたエッチング処理により第1のパターンを形成する工程であることも好ましい。
他の膜形成工程により得られた膜を露光、現像等によりパターン化する方法としては、上述の第1の露光工程、第1の現像工程と同様の方法が挙げられる。
エッチング処理については、公知の方法を参考に行うことができる。
ここで、上記エッチングはドライエッチングであってもウエットエッチングであってもよいが、ドライエッチングであることが好ましい。
また、上記エッチングにより、上記マスクとして使用されたパターンは残存してもよいし、除去されてもよいが、除去されることが好ましい。 [Pattern formation process by etching]
Further, the first pattern forming step includes another film forming step after the first film forming step, and the film obtained by the other film forming step is patterned by exposure, development, or the like, and then the pattern is formed. It is also preferable that the step of forming the first pattern by an etching process using the as a mask.
As a method of patterning the film obtained by other film forming steps by exposure, development, etc., the same methods as the above-described first exposure step and first development step can be mentioned.
Etching can be performed with reference to known methods.
Here, the etching may be dry etching or wet etching, but dry etching is preferable.
Moreover, the pattern used as the mask may remain or be removed by the etching, but is preferably removed.
本発明の永久膜の製造方法は、上記第1のパターンを有する基材上に、第2の樹脂組成物を付与し、第1のパターン上、及び、第1のパターンの間の領域に第2の樹脂組成物の被膜(以下、「第2の樹脂組成物膜」ともいう。)を形成する工程(第2の膜形成工程)を含む。
第2の膜形成工程は、第1のパターンを有する基材上に第2の樹脂組成物を付与するという点以外は、第1の膜形成工程と同様の方法により行うことができる。また、第1の乾燥工程と同様の乾燥工程を、第2の乾燥工程として含んでもよい。
第2の膜形成工程において、第2の樹脂組成物の被膜は、例えば、基材及び第1のパターンの全面に形成することができる。また、第2の樹脂組成物の被膜を、基材及び第1のパターンの一部のみに形成してもよい。
第2の膜形成工程において形成される第2の樹脂組成物の被膜の厚さ(第1のパターン上に形成される被膜の厚さ)は、0.1~20μmであることが好ましく、1~10μmであることがより好ましい。 <Second film formation step>
In the method for producing a permanent film of the present invention, the second resin composition is applied onto the substrate having the first pattern, and the first pattern is formed on the first pattern and in the region between the first patterns. 2 (hereinafter also referred to as “second resin composition film”) (second film forming step).
The second film-forming step can be performed in the same manner as the first film-forming step, except that the second resin composition is applied onto the substrate having the first pattern. Also, a drying step similar to the first drying step may be included as the second drying step.
In the second film forming step, for example, a film of the second resin composition can be formed on the entire surface of the substrate and the first pattern. Also, the coating of the second resin composition may be formed only on a part of the substrate and the first pattern.
The thickness of the film of the second resin composition formed in the second film forming step (the thickness of the film formed on the first pattern) is preferably 0.1 to 20 μm. More preferably ~10 μm.
本発明の永久膜の製造方法は、第2の樹脂組成物の被膜の一部を除去し、第1のパターンと接する第2のパターンを形成する工程を含む。
第2のパターンは、第1のパターンの少なくとも一部と接していればよいが、第1のパターンの側面を少なくとも覆うように形成されることが好ましい。また、第1のパターンの全ての側面に第2のパターンが形成されてもよいし、第1のパターンに存在する複数の側面のうち、一部の側面にのみ第2のパターンが形成されてもよい。
また、アスペクト比を向上させる観点からは、第1のパターンの上面及び側面を覆うように形成されることも好ましい。
第2の樹脂組成物の被膜の除去において、基材の一部が露出するまで除去されることが好ましい。すなわち、第2の樹脂組成物の被膜が除去される領域は、第1のパターンが存在しない領域を少なくとも含むことが好ましい。
本発明において、第2のパターン及び第1のパターンからなるパターンを、複合パターンともいう。 <Second pattern formation step>
The method for producing a permanent film of the present invention includes the step of removing part of the film of the second resin composition to form a second pattern in contact with the first pattern.
The second pattern may be in contact with at least part of the first pattern, but is preferably formed so as to cover at least the side surface of the first pattern. Also, the second pattern may be formed on all side surfaces of the first pattern, or the second pattern may be formed only on some of the plurality of side surfaces of the first pattern. good too.
Moreover, from the viewpoint of improving the aspect ratio, it is also preferable that the first pattern is formed so as to cover the upper surface and side surfaces thereof.
In removing the film of the second resin composition, it is preferably removed until a part of the substrate is exposed. That is, it is preferable that the region from which the film of the second resin composition is removed includes at least a region where the first pattern does not exist.
In the present invention, a pattern consisting of the second pattern and the first pattern is also called a composite pattern.
複合パターンの形状は、パターン間の領域が狭くなる以外は、上述の第1のパターンの形状と同様であることが好ましい。例えば、本発明において、第2の前加熱工程及び現像工程(必要に応じて、第2の後加熱工程)を行うことにより、パターン間の領域が狭くなる以外は、上述の第1のパターンの形状と同様の形状である複合パターンを形成することができる。
例えば、第1のパターンがホールパターンである場合、複合パターンは、第1のパターンよりも直径の小さいホールパターンであることが好ましい。具体的には、ホールパターンである第1のパターンの直径に対して、ホールパターンである複合パターンの直径が、0.1μm以上縮小されることが好ましく、0.3μm以上縮小されることがより好ましく、0.5μm以上縮小されることが更に好ましい。
複合パターンがホールパターンである場合、例えば、直径が0.5~100μmのホールパターンが挙げられ、直径が3~50μmのホールパターンが好ましい。ホールパターンの直径の定義については、上述の通りである。
第1のパターンがトレンチパターンである場合、複合パターンは、第1のパターンよりもトレンチ幅が小さいトレンチパターンであることが好ましい。具体的には、トレンチパターンである第1のパターンのトレンチ幅に対して、トレンチパターンである複合パターンのトレンチ幅が、0.1μm以上縮小されることが好ましく、0.3μm以上縮小されることがより好ましく、0.5μm以上縮小されることが更に好ましい。
複合パターンがトレンチパターンである場合、トレンチ幅が0.5~100μmのトレンチパターンが挙げられ、トレンチ幅が3~50μmのトレンチパターンが好ましい。 The shape of the composite pattern is not particularly limited, but examples thereof include hole patterns (eg, via patterns), trench patterns, and the like.
The shape of the composite pattern is preferably similar to the shape of the first pattern described above, except that the regions between the patterns are narrower. For example, in the present invention, by performing a second pre-heating step and a developing step (if necessary, a second post-heating step), the above-described first pattern except for narrowing the region between the patterns. Composite patterns can be formed that are shaped like shapes.
For example, if the first pattern is a hole pattern, the composite pattern is preferably a hole pattern with a smaller diameter than the first pattern. Specifically, the diameter of the composite pattern, which is the hole pattern, is preferably reduced by 0.1 μm or more, more preferably by 0.3 μm or more, with respect to the diameter of the first pattern, which is the hole pattern. Preferably, it is more preferably reduced by 0.5 μm or more.
When the composite pattern is a hole pattern, for example, a hole pattern with a diameter of 0.5 to 100 μm can be mentioned, and a hole pattern with a diameter of 3 to 50 μm is preferred. The definition of the diameter of the hole pattern is as described above.
When the first pattern is a trench pattern, the composite pattern is preferably a trench pattern with a smaller trench width than the first pattern. Specifically, the trench width of the composite pattern, which is the trench pattern, is preferably reduced by 0.1 μm or more, more preferably by 0.3 μm or more, with respect to the trench width of the first pattern, which is the trench pattern. is more preferable, and it is even more preferable to reduce by 0.5 μm or more.
When the composite pattern is a trench pattern, a trench pattern with a trench width of 0.5 to 100 μm can be mentioned, and a trench pattern with a trench width of 3 to 50 μm is preferred.
第2のパターン形成工程は、第2の膜形成工程により形成された膜(第2の前加熱工程を含む場合、第2の前加熱工程後の膜)を現像液を用いて現像してパターンを形成する第2の現像工程を含むことが好ましい。
ここで、第2の現像工程は、第1の現像工程と同様の方法により行うことができる。ただし、第1の現像工程における「第1のパターン形成工程」、「第1の樹脂組成物」等は、それぞれ、「第2のパターン形成工程」、「第2の樹脂組成物」等に読み替えるものとする。
また、第2の現像工程における現像時間は、1分間~20分間が好ましく、2分間~10分間がより好ましい。
中でも、第2のパターンを形成する工程は、上記第2の樹脂組成物の被膜の一部を溶剤現像により除去する工程であることが好ましい。溶剤現像とは、現像液として有機溶剤を含む現像液を用いた現像をいう。 [Second development step]
In the second pattern forming step, the film formed in the second film forming step (the film after the second preheating step when the second preheating step is included) is developed with a developer to form a pattern. It is preferred to include a second development step to form a
Here, the second development process can be performed by the same method as the first development process. However, "first pattern forming step", "first resin composition", etc. in the first development step should be read as "second pattern forming step", "second resin composition", etc., respectively. shall be
The development time in the second development step is preferably 1 minute to 20 minutes, more preferably 2 minutes to 10 minutes.
Among them, the step of forming the second pattern is preferably a step of removing part of the coating of the second resin composition by solvent development. Solvent development refers to development using a developer containing an organic solvent.
本発明の永久膜の製造方法は、上記第2の樹脂組成物の被膜を形成する工程の後、上記第2のパターンを形成する工程の前に、上記第1のパターン及び上記第2の樹脂組成物の被膜を加熱する工程(第2の前加熱工程)を含んでもよい。
第2の前加熱工程により、例えば、第2の樹脂組成物膜の第2の現像工程における現像液への溶解度を調整し、複合パターンを形成しやすくすることができる。
第2の前加熱工程における加熱は、例えば、上述の第1の加熱工程と同様の方法により行うことができる。
第2の前加熱工程における加熱温度及び加熱時間は、第2の樹脂組成物に含まれる成分、第2の現像工程で用いる現像液等に応じて決定すればよい。
例えば、加熱温度としては、80~180℃が好ましく、90~170℃がより好ましい。 <Second preheating step>
In the method for producing a permanent film of the present invention, after the step of forming a film of the second resin composition and before the step of forming the second pattern, the first pattern and the second resin A step of heating the coating of the composition (second preheating step) may be included.
By the second preheating step, for example, the solubility of the second resin composition film in the developer in the second developing step can be adjusted to facilitate formation of the composite pattern.
Heating in the second preheating step can be performed, for example, by the same method as in the above-described first heating step.
The heating temperature and heating time in the second preheating step may be determined according to the components contained in the second resin composition, the developer used in the second developing step, and the like.
For example, the heating temperature is preferably 80 to 180°C, more preferably 90 to 170°C.
本発明の永久膜の製造方法は、上記第2のパターンを形成する工程の後に、加熱工程(第2の後加熱工程)を更に含むことが好ましい。
特に、第1の樹脂組成物及び第2の樹脂組成物の少なくとも一方がポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、第2の後加熱工程において、ポリイミド前駆体又はポリベンゾオキサゾール前駆体等の樹脂は、環化してポリイミド、ポリベンゾオキサゾール等の樹脂となる。
また、樹脂、又は、樹脂以外の重合性基を有する化合物における未反応の重合性基の架橋なども進行する。
第2の後加熱工程における加熱温度(最高加熱温度)としては、50~350℃が好ましく、150~250℃が更に好ましく、160~250℃が一層好ましく、160~230℃が特に好ましい。 <Second post-heating step>
It is preferable that the method for producing a permanent film of the present invention further includes a heating step (second post-heating step) after the step of forming the second pattern.
In particular, when at least one of the first resin composition and the second resin composition contains a polyimide precursor or a polybenzoxazole precursor, in the second post-heating step, the polyimide precursor, the polybenzoxazole precursor, or the like The resin is cyclized to become a resin such as polyimide or polybenzoxazole.
Moreover, cross-linking of unreacted polymerizable groups in a resin or a compound having a polymerizable group other than a resin also progresses.
The heating temperature (maximum heating temperature) in the second post-heating step is preferably 50 to 350°C, more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。 Heating in the second post-heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 °C/sec is more preferred.
上記加熱温度の上限は、350℃以下であることが好ましく、250℃以下であることがより好ましく、240℃以下であることが更に好ましい。 Especially when forming a multilayer laminate, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.
更に、加熱後冷却してもよく、この場合の冷却速度としては、1~5℃/分であることが好ましい。 Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
第2の後加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。 The second post-heating step is preferably performed in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
The heating means in the second post-heating step is not particularly limited, but examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
また、第2の後加熱工程に代えて、又は、第2の後加熱工程に加えて、第2の後露光工程を含んでもよい。
第2の後露光工程は、上述の、第1の現像後露光工程と同様の方法により行うことができる。 [Second post-exposure step]
Also, a second post-exposure step may be included instead of or in addition to the second post-heating step.
The second post-exposure step can be performed in the same manner as the first post-development exposure step described above.
第2のパターン形成工程により得られた複合パターン(第2の後加熱工程に供されたものが好ましい)は、複合パターン上に金属層を形成する金属層形成工程に供されてもよい。
すなわち、本発明の永久膜の製造方法は、得られた複合パターン(第2の後加熱工程に供されたものが好ましい)上に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
The composite pattern obtained by the second pattern forming step (preferably subjected to the second post-heating step) may be subjected to a metal layer forming step of forming a metal layer on the composite pattern.
That is, the method for producing a permanent film of the present invention preferably includes a metal layer forming step of forming a metal layer on the resulting composite pattern (preferably subjected to the second post-heating step).
本発明の永久膜の製造方法により得られる永久膜(すなわち、複合パターン)は、ポリイミド又はポリベンゾオキサゾールを含むことが好ましい。
ここで、永久膜を形成する第1のパターン及び第2のパターンの少なくとも一方がポリイミド又はポリベンゾオキサゾールを含んでいればよいが、第1のパターン及び第2のパターンの両方がポリイミド又はポリベンゾオキサゾールを含む態様も、本発明の好ましい態様の一つである。
中でも、本発明の永久膜の製造方法により得られる永久膜は、ポリイミドを含むことが好ましい。
この場合、永久膜を形成する第1のパターン及び第2のパターンの少なくとも一方がポリイミドを含んでいればよいが、第1のパターン及び第2のパターンの両方がポリイミドを含む態様も、本発明の好ましい態様の一つである。 <Permanent film>
The permanent film (that is, composite pattern) obtained by the method for producing a permanent film of the present invention preferably contains polyimide or polybenzoxazole.
Here, at least one of the first pattern and the second pattern forming the permanent film should contain polyimide or polybenzoxazole, but both the first pattern and the second pattern may contain polyimide or polybenzoxazole. An embodiment containing oxazole is also one of the preferred embodiments of the present invention.
Especially, it is preferable that the permanent film obtained by the manufacturing method of the permanent film of this invention contains a polyimide.
In this case, at least one of the first pattern and the second pattern that form the permanent film may contain polyimide, but both the first pattern and the second pattern may contain polyimide. It is one of the preferred embodiments of
上記破断伸びは、実施例に示した方法により測定することができる。 Further, the elongation at break of the composite pattern obtained by the method for producing a permanent film of the present invention is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.
The elongation at break can be measured by the method shown in Examples.
第2の樹脂組成物の、下記条件1における比誘電率は、4.0以下であることが好ましく、3.5以下であることがより好ましく、3.0以下であることが更に好ましい。上記比誘電率の下限は特に限定されず、0以上であればよい。
第2の樹脂組成物の、下記条件1における誘電正接は、0.01以下であることが好ましく、0.005以下であることがより好ましく、0.002以下であることが更に好ましい。上記誘電正接の下限は特に限定されず、0以上であればよい。
条件1:組成物を15μmの厚さで表面に酸化膜(SiO2)を形成したシリコンウエハに塗布し、100℃5分間で乾燥し、230℃180分間で加熱して硬化膜を作成し、フッ化水素に浸漬して作成した組成物の単独膜の比誘電率、誘電正接を測定する。
比誘電率及び誘電正接は、JIS(Japanese Industrial Standards)R 1641 「ファインセラミックス基板のマイクロ波誘電特性の測定方法」に従い測定することができる。 [Second pattern]
The dielectric constant of the second resin composition under
The dielectric loss tangent of the second resin composition under
Condition 1: The composition was applied to a silicon wafer having an oxide film (SiO 2 ) formed on the surface to a thickness of 15 μm, dried at 100° C. for 5 minutes, and heated at 230° C. for 180 minutes to form a cured film. The dielectric constant and dielectric loss tangent of a single film of the composition prepared by immersing it in hydrogen fluoride are measured.
The dielectric constant and dielectric loss tangent can be measured according to JIS (Japanese Industrial Standards) R 1641 "Measuring method for microwave dielectric properties of fine ceramic substrates".
本発明の永久膜の製造方法、又は、本発明の永久膜の製造方法により得られた永久膜の適用可能な分野としては、電子デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料(フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜)、又は上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス&テクノロジー(株)「ポリイミドの高機能化と応用技術」2008年4月、柿本雅明/監修、CMCテクニカルライブラリー「ポリイミド材料の基礎と開発」2011年11月発行、日本ポリイミド・芳香族系高分子研究会/編「最新ポリイミド 基礎と応用」エヌ・ティー・エス,2010年8月等を参照することができる。 <Application>
Fields to which the method for producing a permanent film of the present invention or the permanent film obtained by the method for producing a permanent film of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films. etc. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011 Published by the Japan Polyimide and Aromatic Polymer Research Group/Edited, "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.
本発明において、積層体とは、本発明の永久膜の製造方法により得られた永久膜からなる層を複数層有する構造体をいう。
積層体は、永久膜からなる層を2層以上含む積層体であり、3層以上積層した積層体としてもよい。
上記積層体に含まれる2層以上の上記永久膜からなる層のうち、少なくとも1つが本発明の永久膜の製造方法により得られた永久膜からなる層であり、永久膜の収縮、又は、上記収縮に伴う永久膜の変形等を抑制する観点からは、上記積層体に含まれる全ての永久膜からなる層が本発明の永久膜の製造方法により得られた永久膜からなる層であることも好ましい。 (Laminate and method for manufacturing the laminate)
In the present invention, the term "laminate" refers to a structure having a plurality of layers made of the permanent film obtained by the method for producing a permanent film of the present invention.
The laminated body is a laminated body including two or more layers made of permanent films, and may be a laminated body in which three or more layers are laminated.
Of the two or more layers of the permanent film contained in the laminate, at least one is a layer of the permanent film obtained by the method for producing a permanent film of the present invention, and the shrinkage of the permanent film or the above From the viewpoint of suppressing deformation of the permanent film due to shrinkage, all the layers made of the permanent film contained in the laminate may be layers made of the permanent film obtained by the method for producing a permanent film of the present invention. preferable.
すなわち、本発明の積層体の製造方法は、複数回行われる永久膜の製造方法の間に、永久膜からなる層上に金属層を形成する金属層形成工程を更に含むことが好ましい。金属層形成工程の好ましい態様は上述の通りである。
上記積層体としては、例えば、第一の永久膜からなる層、金属層、第二の永久膜からなる層の3つの層がこの順に積層された層構造を少なくとも含む積層体が好ましいものとして挙げられる。
上記第一の永久膜からなる層及び上記第二の永久膜からなる層は、いずれも本発明の永久膜の製造方法により得られた永久膜からなる層であることが好ましい。上記第一の永久膜からなる層の形成に用いられる樹脂組成物と、上記第二の永久膜からなる層の形成に用いられる樹脂組成物とは、組成が同一の組成物であってもよいし、組成が異なる組成物であってもよい。本発明の積層体における金属層は、再配線層などの金属配線として好ましく用いられる。 The laminated body of the present invention preferably includes two or more layers of permanent films, and preferably includes a metal layer between any of the layers of the permanent films. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for manufacturing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the permanent film between the methods for manufacturing the permanent film that are performed multiple times. Preferred aspects of the metal layer forming step are as described above.
As the laminate, for example, a laminate containing at least a layer structure in which three layers, a layer consisting of a first permanent film, a metal layer, and a layer consisting of a second permanent film are laminated in this order, is preferred. be done.
It is preferable that both the layer comprising the first permanent film and the layer comprising the second permanent film are layers comprising a permanent film obtained by the method for producing a permanent film of the present invention. The resin composition used for forming the layer consisting of the first permanent film and the resin composition used for forming the layer consisting of the second permanent film may have the same composition. However, it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.
本発明の積層体の製造方法は、積層工程を含むことが好ましい。
積層工程とは、複合パターン(永久膜)又は金属層の表面に、再度、(a)第1のパターン形成工程、(b)第2の膜形成工程、(c)第2のパターン形成工程を、この順に行うことを含む一連の工程である。必要に応じて、上述の第2の前加熱工程、第2の後加熱工程などを更に行ってもよい。
また、(c)第2のパターン形成工程の後(好ましくは、第2の後加熱工程の後)には(d)金属層形成工程を含んでもよい。積層工程には、更に、上記乾燥工程等を適宜含んでいてもよいことは言うまでもない。 <Lamination process>
It is preferable that the method for manufacturing the laminate of the present invention includes a lamination step.
The lamination step is to repeat (a) the first pattern formation step, (b) the second film formation step, and (c) the second pattern formation step on the surface of the composite pattern (permanent film) or metal layer. , in that order. If necessary, the above-described second preheating step, second postheating step, and the like may be further performed.
In addition, (c) after the second pattern forming step (preferably after the second post-heating step), (d) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
例えば、樹脂層(永久膜)/金属層/樹脂層(永久膜)/金属層/樹脂層(永久膜)/金属層のように、樹脂層(永久膜)を2層以上20層以下とする構成が好ましく、2層以上9層以下とする構成が更に好ましい。
上記各層はそれぞれ、組成、形状、膜厚等が同一であってもよいし、異なっていてもよい。 The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer/resin layer (permanent film)/metal layer, the number of resin layers (permanent film) is 2 or more and 20 or less. The structure is preferable, and the structure with 2 to 9 layers is more preferable.
Each of the above layers may have the same composition, shape, film thickness, etc., or may differ from each other.
本発明の積層体の製造方法は、上記金属層および永久膜の少なくとも一部を表面活性化処理する、表面活性化処理工程を含むことが好ましい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記(c)第2のパターン形成工程の後(好ましくは、第2の後加熱工程の後)、永久膜に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、永久膜の少なくとも一部のみに行ってもよいし、金属層および永久膜の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に永久膜を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる永久膜との密着性を向上させることができる。
また、表面活性化処理は、永久膜の一部または全部についても行うことが好ましい。このように、永久膜の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や永久膜との密着性を向上させることができる。特にネガ型現像を行う場合など、永久膜が硬化されている場合には、表面処理によるダメージを受けにくく、密着性が向上しやすい。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。 (Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least part of the metal layer and the permanent film.
The surface activation treatment step is usually performed after the metal layer formation step, but after the second pattern formation step (c) (preferably after the second post-heating step), the permanent film is surface-activated. After performing the treatment step, the metal layer forming step may be performed.
The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed on at least a portion of the permanent film, or may be performed on at least a portion of both the metal layer and the permanent film. may The surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which a permanent film is to be formed. By subjecting the surface of the metal layer to the surface activation treatment in this way, it is possible to improve the adhesion to the permanent film provided on the surface.
In addition, it is preferable to perform the surface activation treatment on part or all of the permanent film. By subjecting the surface of the permanent film to the surface activation treatment in this way, it is possible to improve the adhesion with the metal layer and the permanent film provided on the surface that has undergone the surface activation treatment. In particular, when the permanent film is hardened, such as when negative development is performed, damage due to surface treatment is less likely to occur, and adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF 4 /O 2 . , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups and thiol groups. The treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound and mechanical surface roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , most preferably 10,000-50,000 J/m 2 .
本発明は、本発明の永久膜の製造方法、又は、本発明の積層体の製造方法を含む半導体デバイスの製造方法も開示する。本発明の永久膜の製造方法により得られた永久膜を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開2016-027357号公報の段落0213~0218の記載及び図1の記載を参酌でき、これらの内容は本明細書に組み込まれる。 (Method for manufacturing semiconductor device)
The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing the permanent film of the present invention or the method for manufacturing the laminate of the present invention. Specific examples of semiconductor devices using the permanent film obtained by the method for producing a permanent film of the present invention for forming an interlayer insulating film for a rewiring layer include the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and The description of FIG. 1 can be referred to, and the contents thereof are incorporated herein.
以下、本発明に係る樹脂組成物に含まれる成分について詳細に説明する。
第1の樹脂組成物と第2の樹脂組成物とは、同一の組成物であってもよいし、組成が異なる組成物であってもよい。 (First resin composition and second resin composition)
Components contained in the resin composition according to the present invention are described in detail below.
The first resin composition and the second resin composition may be the same composition or different compositions.
ネガ型感放射線性樹脂組成物とは、ネガ型感光膜の形成に用いられる組成物である。
中でも、第1の樹脂組成物は、樹脂と、光重合開始剤及び光酸発生剤の少なくとも一方とを含む組成物であることが好ましく、樹脂と、光重合開始剤とを含む組成物であることがより好ましく、樹脂と、光重合開始剤と、重合性化合物とを含む樹脂であることが更に好ましい。
また、第1の樹脂組成物に含まれる樹脂は、ポリイミド前駆体又はポリベンゾオキサゾール前駆体であることが好ましい。
これらの成分については後述する。 The first resin composition is preferably a negative radiation-sensitive resin composition.
A negative radiation-sensitive resin composition is a composition used for forming a negative photosensitive film.
Among them, the first resin composition is preferably a composition containing a resin and at least one of a photopolymerization initiator and a photoacid generator, and is a composition containing a resin and a photopolymerization initiator. More preferably, it is a resin containing a resin, a photopolymerization initiator, and a polymerizable compound.
Moreover, the resin contained in the first resin composition is preferably a polyimide precursor or a polybenzoxazole precursor.
These components are described below.
また、第2の樹脂組成物は、熱重合開始剤を含むことが好ましい。
第2の樹脂組成物は、樹脂として重合性基を有する樹脂を含むことが好ましい。ここで、上記重合性基は、第1の樹脂組成物に含まれる樹脂、又は、重合性化合物と重合を形成可能な基であることが好ましい。例えば、第1次の樹脂組成物がラジカル重合性化合物を含む場合、第2の樹脂組成物は、樹脂としてラジカル重合性基を有する樹脂を含むことが好ましい。
また、第2の樹脂組成物に含まれる樹脂は、ポリイミド前駆体又はポリベンゾオキサゾール前駆体であることが好ましい。
更に、複合パターンにおける第1のパターンと第2のパターン間の密着性の観点からは、第1の樹脂組成物に含まれる樹脂と、第2の樹脂組成物に含まれる樹脂とが同種の樹脂であることも好ましい。例えば、第1の樹脂組成物に含まれる樹脂と、第2の樹脂組成物に含まれる樹脂とがいずれもポリイミド前駆体である態様などが挙げられる。第1の樹脂組成物に含まれる樹脂と、第2の樹脂組成物に含まれる樹脂とがいずれもポリイミド前駆体である場合には、得られる永久膜の破断伸びも向上すると考えられる。
これらの成分については後述する。 The second resin composition is preferably a thermosetting resin composition.
Also, the second resin composition preferably contains a thermal polymerization initiator.
The second resin composition preferably contains a resin having a polymerizable group as the resin. Here, the polymerizable group is preferably a group capable of forming polymerization with the resin contained in the first resin composition or the polymerizable compound. For example, when the primary resin composition contains a radically polymerizable compound, the second resin composition preferably contains a resin having a radically polymerizable group.
Moreover, the resin contained in the second resin composition is preferably a polyimide precursor or a polybenzoxazole precursor.
Furthermore, from the viewpoint of adhesion between the first pattern and the second pattern in the composite pattern, the resin contained in the first resin composition and the resin contained in the second resin composition are the same type of resin. It is also preferable that For example, there is a mode in which both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors. When both the resin contained in the first resin composition and the resin contained in the second resin composition are polyimide precursors, the elongation at break of the obtained permanent film is considered to be improved.
These components are described below.
以下の説明において、単に「樹脂組成物」と記載した場合、第1の樹脂組成物及び第2の樹脂組成物の両方を指すものとする。 The components contained in the first resin composition and the second resin composition are described in detail below.
In the following description, the term "resin composition" simply refers to both the first resin composition and the second resin composition.
樹脂としては、以下に示す、環化樹脂及びその前駆体(特定樹脂)及び他の樹脂が挙げられる。 The resin composition according to the present invention contains a resin.
Examples of resins include cyclized resins and their precursors (specific resins) and other resins shown below.
本発明に係る樹脂組成物は、環化樹脂およびその前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含むことが好ましい。
環化樹脂は、主鎖構造中にイミド環構造又はオキサゾール環構造を含む樹脂であることが好ましい。
本発明において、主鎖とは、樹脂分子中で相対的に最も長い結合鎖を表す。
環化樹脂としては、ポリイミド、ポリベンゾオキサゾール、ポリアミドイミド等が挙げられる。
環化樹脂の前駆体とは、外部刺激により化学構造の変化を生じて環化樹脂となる樹脂をいい、熱により化学構造の変化を生じて環化樹脂となる樹脂が好ましく、熱により閉環反応を生じて環構造が形成されることにより環化樹脂となる樹脂がより好ましい。
環化樹脂の前駆体としては、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリアミドイミド前駆体等が挙げられる。
すなわち、本発明に係る樹脂組成物は、特定樹脂として、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体、ポリアミドイミド、及び、ポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含むことが好ましい。
本発明に係る樹脂組成物は、特定樹脂として、ポリイミド又はポリイミド前駆体を含むことが好ましい。
また、特定樹脂は重合性基を有することが好ましく、ラジカル重合性基を含むことがより好ましい。
特定樹脂がラジカル重合性基を有する場合、本発明に係る樹脂組成物は、後述のラジカル重合開始剤を含むことが好ましく、後述のラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましい。さらに必要に応じて、後述の増感剤を含むことができる。このような本発明に係る樹脂組成物からは、例えば、ネガ型感光膜が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、本発明に係る樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような本発明に係る樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。 <Specific resin>
The resin composition according to the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
In the present invention, the main chain represents the relatively longest connecting chain in the resin molecule.
Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
A precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin. A resin that becomes a cyclized resin by forming a ring structure is more preferable.
Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like.
That is, the resin composition according to the present invention includes, as the specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. resin (specific resin).
The resin composition according to the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the resin composition according to the present invention preferably contains a radical polymerization initiator described later, and includes a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferable. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition according to the present invention.
Moreover, the specific resin may have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition according to the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition according to the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰返し単位を含むことが好ましい。
Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、-Ar-および-Ar-L-Ar-で表される基であることが例示され、特に好ましくは-Ar-L-Ar-で表される基である。但し、Arは、それぞれ独立に、芳香族基であり、Lは、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-若しくは-NHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 A 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
R 111 in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom. may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。 R 111 is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
式中、*は他の構造との結合部位を表す。
In the formula, * represents a binding site with other structures.
式(51)
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(51)又は(61)の構造を与えるジアミンとしては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。 From the viewpoint of i-line transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.
Equation (51)
The monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
このような態様によれば、永久膜の比誘電率を下げることができ、配線の電気抵抗の増大の抑制、永久膜の電気抵抗の低下の抑制等が達成できる場合が有る。
多環の芳香族環構造としては、ビフェニル構造、ターフェニル構造等のポリフェニル構造、ナフタレン環構造、フェナントレン環構造、アントラセン環構造、ピレン環構造、フルオレン環構造、アセナフチレン環構造等が挙げられるが、これに限定されるものではない。
これらの中でも、R111は、ポリフェニル構造又はフルオレン環構造の少なくとも一方を含むことが好ましい。 It is also preferred that R 111 contains a polycyclic aromatic ring structure. In particular, when the second resin composition contains a resin having repeating units represented by formula (2), R 111 also preferably contains a polycyclic aromatic ring structure.
According to this aspect, the dielectric constant of the permanent film can be lowered, and in some cases it is possible to suppress the increase in the electrical resistance of the wiring, the suppression of the decrease in the electrical resistance of the permanent film, and the like.
Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. , but not limited to.
Among these, R 111 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
式(5)又は式(6)中、*はそれぞれ独立に、他の構造との結合部位を表す。
In formula (5) or (6), each * independently represents a binding site to another structure.
多環の芳香族環構造としては、ビフェニル構造、ターフェニル構造等のポリフェニル構造、ナフタレン環構造、フェナントレン環構造、アントラセン環構造、ピレン環構造、フルオレン環構造、アセナフチレン環構造等が挙げられるが、これに限定されるものではない。
これらの中でも、R115は、ポリフェニル構造又はフルオレン環構造の少なくとも一方を含むことが好ましい。 It is also preferred that R 115 contains a polycyclic aromatic ring structure. In particular, when the second resin composition contains a resin having repeating units represented by formula (2), R 115 also preferably contains a polycyclic aromatic ring structure. According to this aspect, the dielectric constant of the permanent film can be lowered, and in some cases it is possible to suppress the increase in the electrical resistance of the wiring, the suppression of the decrease in the electrical resistance of the permanent film, and the like.
Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. , but not limited to.
Among these, R 115 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
エチレン性不飽和結合を有する基としては、ビニル基、アリル基、イソアリル基、2-メチルアリル基、ビニル基と直接結合した芳香環を有する基(例えば、ビニルフェニル基など)、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done. As the radically polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.
Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group. , a (meth)acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
式(III)において、*は他の構造との結合部位を表す。
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-、シクロアルキレン基又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基等のアルキレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基等のアルキレン基、-CH2CH(OH)CH2-、シクロヘキシル基、ポリアルキレンオキシ基がより好ましく、エチレン基、プロピレン基等のアルキレン基、又はポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰返し数の好ましい態様は上述の通りである。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
In formula (III), * represents a binding site with another structure.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R 201 include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 In formula (2), at least one of R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
式(2-A)
Formula (2-A)
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 A 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same. .
R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
上記ポリイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。
また、樹脂組成物が特定樹脂として複数種のポリイミド前駆体を含む場合、少なくとも1種のポリイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In the present specification, the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
Moreover, when the resin composition contains a plurality of polyimide precursors as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the multiple types of polyimide precursors as one resin are within the ranges described above.
本発明に用いられるポリイミドは、アルカリ可溶性ポリイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリイミドであってもよい。
本明細書において、アルカリ可溶性ポリイミドとは、100gの2.38質量%テトラメチルアンモニウム水溶液に対し、23℃で0.1g以上溶解するポリイミドをいい、パターン形成性の観点からは、0.5g以上溶解するポリイミドであることが好ましく、1.0g以上溶解するポリイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、100g以下であることが好ましい。
また、ポリイミドは、得られる有機膜の膜強度及び絶縁性の観点からは、複数個のイミド構造を主鎖に有するポリイミドであることが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。 [Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves at 23° C. by 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.
得られる有機膜の膜強度の観点からは、ポリイミドは、フッ素原子を有することも好ましい。
フッ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にフッ化アルキル基として含まれることがより好ましい。
ポリイミドの全質量に対するフッ素原子の量は、5質量%以上が好ましく、また、20質量%以下が好ましい。 - fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a fluorine atom.
A fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
得られる有機膜の膜強度の観点からは、ポリイミドは、ケイ素原子を有することも好ましい。
ケイ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131に後述する有機変性(ポリ)シロキサン構造として含まれることがより好ましい。
また、上記ケイ素原子又は上記有機変性(ポリ)シロキサン構造はポリイミドの側鎖に含まれていてもよいが、ポリイミドの主鎖に含まれることが好ましい。
ポリイミドの全質量に対するケイ素原子の量は、1質量%以上が好ましく、20質量%以下がより好ましい。 -Silicon atom-
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a silicon atom.
A silicon atom, for example, is preferably contained in R131 in a repeating unit represented by formula (4) described later, and organically modified (poly)siloxane described later in R131 in a repeating unit represented by formula (4) described later More preferably included as a structure.
The silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
得られる有機膜の膜強度の観点からは、ポリイミドは、エチレン性不飽和結合を有することが好ましい。
ポリイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
これらの中でも、エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(IV)で表される基などが挙げられる。 - Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later. It is more preferably included as a group having an ethylenically unsaturated bond in R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by formula (4) described below.
Among these, the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
また、上記炭素数2~12のアルキレン基としては、直鎖状、分岐鎖状、環状又はこれらの組み合わせにより表されるアルキレン基のいずれであってもよい。
上記炭素数2~12のアルキレン基としては、炭素数2~8のアルキレン基が好ましく、炭素数2~4のアルキレン基がより好ましい。 In formula (IV), R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C(═O)O—, —O(C═O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
In addition, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
式(R1)~(R3)中、Lにおける炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様は、上述のR21における、炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様と同様である。
式(R1)中、Xは酸素原子であることが好ましい。
式(R1)~(R3)中、*は式(IV)中の*と同義であり、好ましい態様も同様である。
式(R1)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物(例えば、2-イソシアナトエチルメタクリレート等)とを反応することにより得られる。
式(R2)で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物(例えば、2-ヒドロキシエチルメタクリレート等)とを反応することにより得られる。
式(R3)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物(例えば、グリシジルメタクリレート等)とを反応することにより得られる。 Among these, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
ポリイミドは、エチレン性不飽和結合を有する基以外の重合性基を有していてもよい。
エチレン性不飽和結合を有する基以外の重合性基としては、エポキシ基、オキセタニル基等の環状エーテル基、メトキシメチル基等のアルコキシメチル基、メチロール基等が挙げられる。
エチレン性不飽和結合を有する基以外の重合性基は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するエチレン性不飽和結合を有する基以外の重合性基の量は、0.0001~0.1mol/gであることが好ましく、0.001~0.05mol/gであることがより好ましい。 -Polymerizable Groups Other than Groups Having Ethylenically Unsaturated Bonds-
Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
A polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
The amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
ポリイミドは、酸分解性基等の極性変換基を有していてもよい。ポリイミドにおける酸分解性基は、上述の式(2)におけるR113及びR114において説明した酸分解性基と同様であり、好ましい態様も同様である。
極性変換基は、例えば、後述する式(4)で表される繰返し単位におけるR131、R132、ポリイミドの末端などに含まれる。 -Polarity conversion group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described below, the terminal of polyimide, and the like.
ポリイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリイミドの酸価は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましく、70mgKOH/g以上であることが更に好ましい。
また、上記酸価は500mgKOH/g以下であることが好ましく、400mgKOH/g以下であることがより好ましく、200mgKOH/g以下であることが更に好ましい。
また、ポリイミドが有機溶剤を主成分とする現像液を用いた現像(例えば、後述する「溶剤現像」)に供される場合、ポリイミドの酸価は、1~35mgKOH/gが好ましく、2~30mgKOH/gがより好ましく、5~20mgKOH/gが更に好ましい。
上記酸価は、公知の方法により測定され、例えば、JIS K 0070:1992に記載の方法により測定される。
また、ポリイミドに含まれる酸基としては、保存安定性及び現像性の両立の観点から、pKaが0~10である酸基が好ましく、3~8である酸基がより好ましい。
pKaとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。本明細書において、pKaは、特に断らない限り、ACD/ChemSketch(登録商標)による計算値とする。又は、日本化学会編「改定5版 化学便覧 基礎編」に掲載の値を参照してもよい。
また、酸基が例えばリン酸等の多価の酸である場合、上記pKaは第一解離定数である。
このような酸基として、ポリイミドは、カルボキシ基、及び、フェノール性ヒドロキシ基よりなる群から選ばれた少なくとも1種を含むことが好ましく、フェノール性ヒドロキシ基を含むことがより好ましい。 - Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH. /g is more preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
Considering the dissociation reaction in which hydrogen ions are released from an acid, the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, it is possible to refer to the values listed in the Chemical Society of Japan, "Fifth Revised Edition, Chemistry Handbook, Fundamentals".
Also, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
アルカリ現像液による現像速度を適切なものとする観点からは、ポリイミドは、フェノール性ヒドロキシ基を有することが好ましい。
ポリイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
フェノール性ヒドロキシ基は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するフェノール性ヒドロキシ基の量は、0.1~30mol/gであることが好ましく、1~20mol/gであることがより好ましい。 -Phenolic hydroxy group-
The polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
The polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
The amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
重合性基を有する場合、重合性基は、R131及びR132の少なくとも一方に位置していてもよいし、下記式(4-1)又は式(4-2)に示すようにポリイミドの末端に位置していてもよい。
式(4-1)
式(4-2)
When it has a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in
Formula (4-1)
Formula (4-2)
R131は、2価の有機基を表す。2価の有機基としては、式(2)におけるR111と同様のものが例示され、好ましい範囲も同様である。
また、R131としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族又は芳香族ジアミンなどが挙げられる。具体的な例としては、ポリイミド前駆体の式(2)中のR111の例が挙げられる。 Examples of the polymerizable group include the above-described groups containing an ethylenically unsaturated bond and crosslinkable groups other than the above-described groups having an ethylenically unsaturated bond.
R 131 represents a divalent organic group. Examples of the divalent organic group are the same as those of R 111 in formula (2), and the preferred range is also the same.
R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R 111 in formula (2) of the polyimide precursor.
例えば、R115として例示される4価の有機基の4つの結合子が、上記式(4)中の4つの-C(=O)-の部分と結合して縮合環を形成する。 R 132 represents a tetravalent organic group. Examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
For example, four bonds of a tetravalent organic group exemplified as R 115 combine with four —C(═O)— moieties in the above formula (4) to form a condensed ring.
ポリイミドのイミド化率(「閉環率」ともいう)は、得られる有機膜の膜強度、絶縁性等の観点からは、70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることがより好ましい。
上記イミド化率の上限は特に限定されず、100%以下であればよい。
上記イミド化率は、例えば下記方法により測定される。
ポリイミドの赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求める。次に、そのポリイミドを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求める。得られたピーク強度P1、P2を用い、下記式に基づいて、ポリイミドのイミド化率を求めることができる。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100 -Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm −1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm −1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100
また、ポリイミドの数平均分子量(Mn)は、好ましくは2,000~40,000であり、より好ましくは3,000~30,000であり、更に好ましくは4,000~20,000である。
上記ポリイミドの分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリイミドの分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
また、樹脂組成物が特定樹脂として複数種のポリイミドを含む場合、少なくとも1種のポリイミドの重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミドを1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break).
Also, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide molecular weight dispersion is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
Moreover, when the resin composition contains a plurality of types of polyimide as the specific resin, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural kinds of polyimides as one resin are within the ranges described above.
本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰返し単位を含む。
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。 In formula (3), R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a linear aliphatic group is preferred. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。 As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, thoria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.
R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
R 122 is also preferably a group derived from a bisaminophenol derivative. -diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino- 4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, 4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination.
ポリベンゾオキサゾール前駆体は、閉環に伴う反りの発生を抑制できる点で、下記式(SL)で表されるジアミン残基を他の種類の繰返し単位として含むことが好ましい。 The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of formula (3) above.
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。
また、樹脂組成物が特定樹脂として複数種のポリベンゾオキサゾール前駆体を含む場合、少なくとも1種のポリベンゾオキサゾール前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリベンゾオキサゾール前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
In addition, when the resin composition contains multiple types of polybenzoxazole precursors as specific resins, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the above plural kinds of polybenzoxazole precursors as one resin are within the ranges described above.
ポリベンゾオキサゾールとしては、ベンゾオキサゾール環を有する高分子化合物であれば、特に限定はないが、下記式(X)で表される化合物であることが好ましく、下記式(X)で表される化合物であって、重合性基を有する化合物であることがより好ましい。上記重合性基としては、ラジカル重合性基が好ましい。また、下記式(X)で表される化合物であって、酸分解性基等の極性変換基を有する化合物であってもよい。
重合性基又は酸分解性基等の極性変換基を有する場合、重合性基又は酸分解性基等の極性変換基は、R133及びR134の少なくとも一方に位置していてもよいし、下記式(X-1)又は式(X-2)に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式(X-1)
式(X-2)
Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group. As the polymerizable group, a radically polymerizable group is preferred. Further, it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.
In the case of having a polar conversion group such as a polymerizable group or an acid-decomposable group, the polar conversion group such as a polymerizable group or an acid-decomposable group may be positioned at least one of R 133 and R 134 . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
Formula (X-1)
Formula (X-2)
例えば、R122として例示される4価の有機基の4つの結合子が、上記式(X)中の窒素原子、酸素原子と結合して縮合環を形成する。例えば、R134が、下記有機基である場合、下記構造を形成する。下記構造中、*はそれぞれ、式(X)中の窒素原子又は酸素原子との結合部位を表す。
For example, four bonds of a tetravalent organic group exemplified as R 122 combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).
上記オキサゾール化率は、例えば下記方法により測定される。
ポリベンゾオキサゾールの赤外吸収スペクトルを測定し、前駆体のアミド構造に由来する吸収ピークである1650cm-1付近のピーク強度Q1を求める。次に、1490cm-1付近に見られる芳香環の吸収強度で規格化する。そのポリベンゾオキサゾールを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1650cm-1付近のピーク強度Q2を求め、1490cm-1付近に見られる芳香環の吸収強度で規格化する。得られたピーク強度Q1、Q2の規格値を用い、下記式に基づいて、ポリベンゾオキサゾールのオキサゾール化率を求めることができる。
オキサゾール化率(%)=(ピーク強度Q1の規格値/ピーク強度Q2の規格値)×100 Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when the film is oxazolized by heating can be reduced, and the occurrence of warpage can be more effectively suppressed.
The oxazolization rate is measured, for example, by the method described below.
The infrared absorption spectrum of polybenzoxazole is measured, and the peak intensity Q1 near 1650 cm −1 , which is the absorption peak derived from the amide structure of the precursor, is determined. Next, normalization is performed by the absorption intensity of the aromatic ring seen around 1490 cm −1 . After heat-treating the polybenzoxazole at 350° C. for 1 hour, the infrared absorption spectrum is measured again, the peak intensity Q2 near 1650 cm −1 is obtained, and the absorption intensity of the aromatic ring seen near 1490 cm −1 is normalized. do. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazole conversion rate of polybenzoxazole can be obtained based on the following formula.
Oxazolization rate (%) = (standardized value of peak intensity Q1/standardized value of peak intensity Q2) x 100
なお、ジカルボン酸の場合には反応収率等を高めるため、1-ヒドロキシ-1,2,3-ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。 Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
In the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.
また、ポリベンゾオキサゾールの数平均分子量(Mn)は、好ましくは7,200~14,000であり、より好ましくは8,000~12,000であり、更に好ましくは9,200~11,200である。
上記ポリベンゾオキサゾールの分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾールの分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。
また、樹脂組成物が特定樹脂として複数種のポリベンゾオキサゾールを含む場合、少なくとも1種のポリベンゾオキサゾールの重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリベンゾオキサゾールを1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
Further, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
The polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.
Moreover, when the resin composition contains a plurality of types of polybenzoxazole as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are within the ranges described above.
ポリアミドイミド前駆体は、下記式(PAI-2)で表される繰返し単位を含むことが好ましい。
The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-2), R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two The above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. or a group in which two or more of these are combined by a single bond or a linking group is preferable, an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group A group obtained by combining two or more of is more preferable.
The linking group includes -O-, -S-, -C(=O)-, -S(=O) 2 -, an alkylene group, a halogenated alkylene group, an arylene group, or two or more of these linked groups. is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are linked is more preferred.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Further, the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
本発明において、カルボキシ基を3つ有する化合物をトリカルボン酸化合物という。
上記トリカルボン酸化合物の3つのカルボキシ基のうち2つのカルボキシ基は酸無水物化されていてもよい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいトリカルボン酸化合物としては、分岐鎖状の脂肪族、環状の脂肪族又は芳香族のトリカルボン酸化合物などが挙げられる。
これらのトリカルボン酸化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Also, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound.
Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
Examples of the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.
これらの化合物は、2つのカルボキシ基が無水物化した化合物(例えば、トリメリット酸無水物)であってもよいし、少なくとも1つのカルボキシ基がハロゲン化した化合物(例えば、無水トリメリット酸クロリド)であってもよい。 Further, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group Linked compounds and the like are included.
These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
他の繰返し単位としては、上述の式(2)で表される繰返し単位、下記式(PAI-1)で表される繰返し単位等が挙げられる。
Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).
式(PAI-1)中、R116は、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又は単結合若しくは連結基によりこれらを2以上連結した基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、単結合若しくは連結基によりこれらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基、又は、単結合若しくは連結基により炭素数6~20の芳香族基を2以上組み合わせた基がより好ましい。
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-1), R 116 represents a divalent organic group and R 111 represents a divalent organic group.
In formula (PAI-1), R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two The above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. or a group in which two or more of these are combined by a single bond or a linking group is preferable, an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group A group obtained by combining two or more of is more preferable.
The linking group includes -O-, -S-, -C(=O)-, -S(=O) 2 -, an alkylene group, a halogenated alkylene group, an arylene group, or two or more of these linked groups. is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are linked is more preferred.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Further, the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
本発明において、カルボキシ基を2つ有する化合物をジカルボン酸化合物、ハロゲン化されたカルボキシ基を2つ有する化合物をジカルボン酸ジハライド化合物という。
ジカルボン酸ジハライド化合物におけるカルボキシ基は、ハロゲン化されていればよいが、例えば、塩素化されていることが好ましい。すなわち、ジカルボン酸ジハライド化合物は、ジカルボン酸ジクロリド化合物であることが好ましい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいジカルボン酸化合物又はジカルボン酸ジハライド化合物としては、直鎖状又は分岐鎖状の脂肪族、環状の脂肪族又は芳香族ジカルボン酸化合物又はジカルボン酸ジハライド化合物などが挙げられる。
これらのジカルボン酸化合物又はジカルボン酸ジハライド化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Also, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
The optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include acid dihalide compounds.
One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
ジカルボン酸ジハライド化合物の具体例としては、上記ジカルボン酸化合物の具体例における2つのカルボキシ基をハロゲン化した構造の化合物が挙げられる。 Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane diacid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontane diacid acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenylcarboxylic acid, 4,4′-biphenylcarboxylic acid, 4,4′- dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid and the like.
Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxy groups in the above specific examples of dicarboxylic acid compounds are halogenated.
また、本発明におけるポリアミドイミド前駆体の別の一実施形態として、式(PAI-2)で表される繰返し単位、及び、式(PAI-1)で表される繰返し単位の合計含有量が、全繰返し単位の50モル%以上である態様が挙げられる。上記合計含有量は、70モル%以上であることがより好ましく、90モル%以上であることが更に好ましく、90モル%超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリアミドイミド前駆体における全ての繰返し単位が、式(PAI-2)で表される繰返し単位、又は、式(PAI-1)で表される繰返し単位のいずれかであってもよい。 As one embodiment of the polyamideimide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by formula (2).
Further, as another embodiment of the polyamideimide precursor in the present invention, the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
ポリアミドイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリアミドイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。また、樹脂組成物が特定樹脂として複数種のポリアミドイミド前駆体を含む場合、少なくとも1種のポリアミドイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリアミドイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. . Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
The polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Further, when the resin composition contains a plurality of types of polyamideimide precursors as specific resins, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
本発明に用いられるポリアミドイミドは、アルカリ可溶性ポリアミドイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリアミドイミドであってもよい。
本明細書において、アルカリ可溶性ポリアミドイミドとは、100gの2.38質量%テトラメチルアンモニウム水溶液に対し、23℃で0.1g以上溶解するポリアミドイミドをいい、パターン形成性の観点からは、0.5g以上溶解するポリアミドイミドであることが好ましく、1.0g以上溶解するポリアミドイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、100g以下であることが好ましい。
また、ポリアミドイミドは、得られる有機膜の膜強度及び絶縁性の観点からは、複数個のアミド結合及び複数個のイミド構造を主鎖に有するポリアミドイミドであることが好ましい。 [Polyamideimide]
The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution. A polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film to be obtained.
得られる有機膜の膜強度の観点からは、ポリアミドイミドは、フッ素原子を有することが好ましい。
フッ素原子は、例えば、後述する式(PAI-3)で表される繰返し単位におけるR117、又は、R111に含まれることが好ましく、後述する式(PAI-3)で表される繰返し単位におけるR117、又は、R111にフッ化アルキル基として含まれることがより好ましい。
ポリアミドイミドの全質量に対するフッ素原子の量は、5質量%以上が好ましく、また、20質量%以下が好ましい。 - Fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyamideimide preferably has a fluorine atom.
A fluorine atom is preferably contained in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R 117 or R 111 as a fluorinated alkyl group.
The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.
得られる有機膜の膜強度の観点からは、ポリアミドイミドは、エチレン性不飽和結合を有してもよい。
ポリアミドイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
エチレン性不飽和結合は、後述する式(PAI-3)で表される繰返し単位におけるR117、又は、R111に含まれることが好ましく、後述する式(PAI-3)で表される繰返し単位におけるR117、又は、R111にエチレン性不飽和結合を有する基として含まれることがより好ましい。
エチレン性不飽和結合を有する基の好ましい態様は、上述のポリイミドにおけるエチレン性不飽和結合を有する基の好ましい態様と同様である。 - Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyamideimide may have an ethylenically unsaturated bond.
The polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, preferably in the side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and the repeating unit represented by formula (PAI-3) described later. It is more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in .
Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.
ポリアミドイミドは、エチレン性不飽和結合以外の重合性基を有していてもよい。
ポリアミドイミドにおけるエチレン性不飽和結合以外の重合性基としては、上述のポリイミドにおけるエチレン性不飽和結合以外の重合性基と同様の基が挙げられる。
エチレン性不飽和結合以外の重合性基は、例えば、後述する式(PAI-3)で表される繰返し単位におけるR111に含まれることが好ましい。
ポリアミドイミドの全質量に対するエチレン性不飽和結合以外の重合性基の量は、0.05~10mol/gであることが好ましく、0.1~5mol/gであることがより好ましい。 -Polymerizable group other than ethylenically unsaturated bond-
Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
Examples of the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the above polymerizable groups other than the ethylenically unsaturated bond in the polyimide.
A polymerizable group other than an ethylenically unsaturated bond is preferably included in R 111 in a repeating unit represented by formula (PAI-3) described later, for example.
The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.
ポリアミドイミドは、酸分解性基等の極性変換基を有していてもよい。ポリアミドイミドにおける酸分解性基は、上述の式(2)におけるR113及びR114において説明した酸分解性基と同様であり、好ましい態様も同様である。 -Polarity conversion group-
Polyamideimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
ポリアミドイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリアミドイミドの酸価は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましく、70mgKOH/g以上であることが更に好ましい。
また、上記酸価は500mgKOH/g以下であることが好ましく、400mgKOH/g以下であることがより好ましく、200mgKOH/g以下であることが更に好ましい。
また、ポリアミドイミドが有機溶剤を主成分とする現像液を用いた現像(例えば、後述する「溶剤現像」)に供される場合、ポリアミドイミドの酸価は、2~35mgKOH/gが好ましく、3~30mgKOH/gがより好ましく、5~20mgKOH/gが更に好ましい。
上記酸価は、公知の方法により測定され、例えば、JIS K 0070:1992に記載の方法により測定される。
また、ポリアミドイミドに含まれる酸基としては、上述のポリイミドにおける酸基と同様の基が挙げられ、好ましい態様も同様である。 - Acid value -
When the polyamideimide is subjected to alkali development, the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more is more preferable.
Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, 3 ~30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
Moreover, as the acid group contained in the polyamideimide, the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.
アルカリ現像液による現像速度を適切なものとする観点からは、ポリアミドイミドは、フェノール性ヒドロキシ基を有することが好ましい。
ポリアミドイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
フェノール性ヒドロキシ基は、例えば、後述する式(PAI-3)で表される繰返し単位におけるR117、又は、R111に含まれることが好ましい。
ポリアミドイミドの全質量に対するフェノール性ヒドロキシ基の量は、0.1~30mol/gであることが好ましく、1~20mol/gであることがより好ましい。 -Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxy group.
Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably included in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later.
The amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
重合性基を有する場合、重合性基は、R111及びR117の少なくとも一方に位置していてもよいし、ポリアミドイミドの末端に位置していてもよい。 The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).
When having a polymerizable group, the polymerizable group may be located at least one of R 111 and R 117 , or may be located at the end of the polyamideimide.
ポリアミドイミドのイミド化率(「閉環率」ともいう)は、得られる有機膜の膜強度、絶縁性等の観点からは、70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることがより好ましい。
上記イミド化率の上限は特に限定されず、100%以下であればよい。
上記イミド化率は、上述のポリイミドの閉環率と同様の方法により測定される。 -Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
また、ポリアミドイミドの数平均分子量(Mn)は、好ましくは800~250,000であり、より好ましくは、2,000~50,000であり、更に好ましくは、4,000~25,000である。
ポリアミドイミドの分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリアミドイミドの分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
また、樹脂組成物が特定樹脂として複数種のポリアミドイミドを含む場合、少なくとも1種のポリアミドイミドの重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリアミドイミドを1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.
Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
The polyamidoimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyamidoimide molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
Moreover, when the resin composition contains a plurality of types of polyamideimide as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.
ポリイミド前駆体等は、例えば、低温中でテトラカルボン酸二無水物とジアミンを反応させる方法、低温中でテトラカルボン酸二無水物とジアミンを反応させてポリアミック酸を得、縮合剤又はアルキル化剤を用いてエステル化する方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得て、その後ジアミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法、などの方法を利用して得ることができる。上記製造方法のうち、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法がより好ましい。
上記縮合剤としては、例えばジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エトキシカルボニル-2-エトキシ-1,2-ジヒドロキノリン、1,1-カルボニルジオキシ-ジ-1,2,3-ベンゾトリアゾール、N,N’-ジスクシンイミジルカーボネート、無水トリフルオロ酢酸等が挙げられる。
上記アルキル化剤としては、N,N-ジメチルホルムアミドジメチルアセタール、N,N-ジメチルホルムアミドジエチルアセタール、N,N-ジアルキルホルムアミドジアルキルアセタール、オルトギ酸トリメチル、オルトギ酸トリエチル等が挙げられる。
上記ハロゲン化剤としては、塩化チオニル、塩化オキサリル、オキシ塩化リン等が挙げられる。
ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン、N-エチルピロリドン、プロピオン酸エチル、ジメチルアセトアミド、ジメチルホルムアミド、テトラヒドロフラン、γ-ブチロラクトン等が例示される。
ポリイミド前駆体等の製造方法では、反応に際し、塩基性化合物を添加することが好ましい。塩基性化合物は1種でもよいし、2種以上でもよい。
塩基性化合物は、原料に応じて適宜定めることができるが、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン、1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、N,N-ジメチル-4-アミノピリジン等が例示される。 [Method for producing polyimide precursor, etc.]
Polyimide precursors and the like, for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
The organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and the like. is exemplified.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. One type of basic compound may be used, or two or more types may be used.
The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、ポリイミド前駆体等の樹脂末端に残存するカルボン酸無水物、酸無水物誘導体、或いは、アミノ基を封止することが好ましい。樹脂末端に残存するカルボン酸無水物、及び酸無水物誘導体を封止する際、末端封止剤としては、モノアルコール、フェノール、チオール、チオフェノール、モノアミン等が挙げられ、反応性、膜の安定性から、モノアルコール、フェノール類やモノアミンを用いることがより好ましい。モノアルコールの好ましい化合物としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、ドデシノール、ベンジルアルコール、2-フェニルエタノール、2-メトキシエタノール、2-クロロメタノール、フルフリルアルコール等の1級アルコール、イソプロパノール、2-ブタノール、シクロヘキシルアルコール、シクロペンタノール、1-メトキシ-2-プロパノール等の2級アルコール、t-ブチルアルコール、アダマンタンアルコール等の3級アルコールが挙げられる。フェノール類の好ましい化合物としては、フェノール、メトキシフェノール、メチルフェノール、ナフタレン-1-オール、ナフタレン-2-オール、ヒドロキシスチレン等のフェノール類などが挙げられる。また、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。
また、樹脂末端のアミノ基を封止する際、アミノ基と反応可能な官能基を有する化合物で封止することが可能である。アミノ基に対する好ましい封止剤は、カルボン酸無水物、カルボン酸クロリド、カルボン酸ブロミド、スルホン酸クロリド、無水スルホン酸、スルホン酸カルボン酸無水物などが好ましく、カルボン酸無水物、カルボン酸クロリドがより好ましい。カルボン酸無水物の好ましい化合物としては、無水酢酸、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸、5-ノルボルネン-2,3-ジカルボン酸無水物などが挙げられる。また、カルボン酸クロリドの好ましい化合物としては、塩化アセチル、アクリル酸クロリド、プロピオニルクロリド、メタクリル酸クロリド、ピバロイルクロリド、シクロヘキサンカルボニルクロリド、2-エチルヘキサノイルクロリド、シンナモイルクロリド、1-アダマンタンカルボニルクロリド、ヘプタフルオロブチリルクロリド、ステアリン酸クロリド、ベンゾイルクロリド、などが挙げられる。 -Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, it is preferable to seal the carboxylic anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as polyimide precursors. When blocking carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of resins, terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
Moreover, when blocking the amino group at the terminal of the resin, it is possible to block with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. are mentioned. Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中に共存している脱水縮合剤の吸水副生物を必要に応じて濾別した後、水、脂肪族低級アルコール、又はその混合液等の貧溶媒に、得られた重合体成分を投入し、重合体成分を析出させることで、固体として析出させ、乾燥させることでポリイミド前駆体等を得ることができる。精製度を向上させるために、ポリイミド前駆体等を再溶解、再沈析出、乾燥等の操作を繰返してもよい。さらに、イオン交換樹脂を用いてイオン性不純物を除去する工程を含んでいてもよい。 -Solid precipitation-
A step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
本発明に係る樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明に係る樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明に係る樹脂組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the resin composition according to the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. It is more preferable that the content is 50% by mass or more. Further, the content of the resin in the resin composition according to the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the resin composition. It is more preferably 97% by mass or less, even more preferably 95% by mass or less.
The resin composition according to the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
具体的には、本発明に係る樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
本発明に係る樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。 Also, the resin composition according to the present invention preferably contains at least two resins.
Specifically, the resin composition according to the present invention may contain a total of two or more kinds of the specific resin and another resin described later, or may contain two or more kinds of the specific resin. It is preferable to include two or more kinds of.
When the resin composition according to the present invention contains two or more specific resins, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a polyimide precursor.
本発明に係る樹脂組成物は、樹脂として、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)を含んでもよい。
また、特定樹脂と、他の樹脂とを含む態様とすることもできる。
他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
例えば、(メタ)アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン(硬化物)が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高い(例えば、樹脂1gにおける重合性基の含有モル量が1×10-3モル/g以上である)(メタ)アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン(硬化物)の耐溶剤性等を向上させることができる。 <Other resins>
The resin composition according to the present invention may contain, as a resin, a resin different from the specific resin (hereinafter also simply referred to as "another resin").
Moreover, it can also be set as the aspect containing specific resin and other resin.
Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable group value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group in 1 g of the resin is 1×10 −3 mol/g or more), the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
本発明に係る樹脂組成物における他の樹脂の含有量は、樹脂組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明に係る樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
また、本発明に係る樹脂組成物が特定樹脂と他の樹脂とを含む場合、他の樹脂の含有量は、樹脂組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましく、40質量%以下、更には、30質量%以下とすることもできる。
また、本発明に係る樹脂組成物の好ましい一態様として、特定樹脂を含み、かつ、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、樹脂組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明に係る樹脂組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition according to the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and 10% by mass or more. Even more preferred.
The content of the other resin in the resin composition according to the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. and more preferably 50% by mass or more. In addition, the content of the resin in the resin composition according to the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the resin composition. It is more preferably 97% by mass or less, even more preferably 95% by mass or less.
Further, when the resin composition according to the present invention contains a specific resin and another resin, the content of the other resin is preferably 80% by mass or less with respect to the total solid content of the resin composition, and 75% by mass. It is more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 50% by mass or less, 40% by mass or less, and further can also be 30% by mass or less.
Further, as a preferred embodiment of the resin composition according to the present invention, it is possible to adopt an embodiment in which the specific resin is included and the content of the other resin is low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The resin composition according to the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
フェノール樹脂としては、レゾール型、ノボラック型のいずれでもよく、具体的には、クレゾールノボラック樹脂、カテコールノボラック樹脂、レゾルシノールノボラック樹脂、ヒドロキノンノボラック、カテコールレゾルシノールノボラック樹脂、レゾルシノールヒドロキノンノボラック樹脂等が挙げられる。
エポキシ樹脂としては、特に限定されないが、ノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、トリフェノールプロパン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレン骨格及びビフェニレン骨格の少なくともいずれかを有するフェノールアラルキル型エポキシ樹脂、フェニレン骨格及びビフェニレン骨格の少なくともいずれかを有するナフトールアラルキル型エポキシ樹脂などのアラルキル型エポキシ樹脂、並びに脂肪族エポキシ樹脂等が挙げられる。 Among these, the resin composition according to the present invention preferably contains at least one resin selected from the group consisting of specific resins, phenolic resins, and epoxy resins.
The phenolic resin may be either resole type or novolak type, and specific examples include cresol novolac resin, catechol novolak resin, resorcinol novolak resin, hydroquinone novolak resin, catechol resorcinol novolac resin, resorcinol hydroquinone novolac resin, and the like.
Epoxy resins are not particularly limited, but are novolac type epoxy resins, bisphenol type epoxy resins, glycidylamine type epoxy resins, glycidyl ether type epoxy resins, triphenolmethane type epoxy resins, triphenolpropane type epoxy resins, alkyl-modified triphenols. methane-type epoxy resin, triazine-nucleus-containing epoxy resin, dicyclopentadiene-modified phenol-type epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, phenol-aralkyl-type epoxy resin having at least one of a phenylene skeleton and a biphenylene skeleton, a phenylene skeleton and Examples include aralkyl epoxy resins such as naphthol aralkyl epoxy resins having at least one biphenylene skeleton, and aliphatic epoxy resins.
本発明に係る樹脂組成物は、重合性化合物を含むことが好ましい。
重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Polymerizable compound>
The resin composition according to the present invention preferably contains a polymerizable compound.
Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
第2の樹脂組成物上には配線(銅等)が配置されることから、配線と直接接する第2の樹脂組成物自身は、配線の電気的性能を向上するような特性が好まれ、例えば、低誘電率となる第2の樹脂組成物が好ましい。そのため、第2の樹脂組成物に含まれる化合物は、フルオレン骨格、ポリフェニレン骨格などの芳香族多環構造を含む化合物、4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビフェニル、4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物などのフッ素含有化合物、又は、ジメチルシロキサン、メチルフェニルシロキサン、ジフェニルシロキサン等に由来するシロキサン基を有する化合物を含む、それ自身で膜を形成した時の比誘電率が3.0よりも低いものが好ましく、2.8以下であることがより好ましく、2.6以下であることが更に好ましい。上記比誘電率の下限は特に限定されず、0以上であればよい。
上記化合物で膜を形成した時の誘電正接は、0.01以下であることが好ましく、0.005以下であることがより好ましく、0.002以下であることが更に好ましい。上記誘電正接の下限は特に限定されず、0以上であればよい。
このようなことから、第2の樹脂組成物は、重合性基及び芳香族多環構造を含む化合物を含むことが好ましく、重合性基及びフルオレン骨格を有する化合物を含むことがより好ましい。
ここで、上記化合物の誘電率は、第2の樹脂組成物に含まれる樹脂誘電率よりも小さいことが好ましい。
具体的には、上記樹脂で膜を形成した時の誘電率と上記化合物で膜を形成した時の比誘電率の差が、0.2以上であることが好ましく、0.4以上であることが更に好ましい。 Moreover, the resin composition (particularly, the second resin composition) according to the present invention preferably contains a compound containing an aromatic polycyclic structure, a fluorine-containing compound, or a compound having a siloxane group.
Since wiring (copper, etc.) is arranged on the second resin composition, the second resin composition itself, which is in direct contact with the wiring, preferably has properties that improve the electrical performance of the wiring. , the second resin composition having a low dielectric constant is preferred. Therefore, the compounds contained in the second resin composition include compounds containing aromatic polycyclic structures such as fluorene skeletons and polyphenylene skeletons, 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl, Fluorine-containing compounds such as 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, or compounds with siloxane groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc., which form films themselves It preferably has a relative dielectric constant of less than 3.0, more preferably 2.8 or less, even more preferably 2.6 or less. The lower limit of the dielectric constant is not particularly limited, and may be 0 or more.
The dielectric loss tangent of the film formed from the compound is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less. The lower limit of the dielectric loss tangent is not particularly limited as long as it is 0 or more.
For this reason, the second resin composition preferably contains a compound containing a polymerizable group and an aromatic polycyclic structure, and more preferably contains a compound having a polymerizable group and a fluorene skeleton.
Here, the dielectric constant of the compound is preferably smaller than the dielectric constant of the resin contained in the second resin composition.
Specifically, the difference between the dielectric constant when the film is formed from the resin and the relative dielectric constant when the film is formed from the compound is preferably 0.2 or more, and preferably 0.4 or more. is more preferred.
上記芳香族多環構造としては、ビフェニル構造、ターフェニル構造等のポリフェニル構造、ナフタレン環構造、フェナントレン環構造、アントラセン環構造、ピレン環構造、フルオレン環構造、アセナフチレン環構造等が挙げられるが、これに限定されるものではない。 The aromatic group in the polymerizable compound having an aromatic group may be monocyclic or polycyclic, preferably polycyclic, more preferably condensed ring.
Examples of the aromatic polycyclic structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. It is not limited to this.
本発明に係る樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基、マレイミド基、(メタ)アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、(メタ)アクリロイル基がより好ましい。 [Radical cross-linking agent]
The resin composition according to the present invention preferably contains a radical cross-linking agent.
A radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
上記エチレン性不飽和結合を2個以上有する化合物としては、エチレン性不飽和結合を2~15個有する化合物が好ましく、エチレン性不飽和結合を2~10個有する化合物がより好ましく、2~6個有する化合物が更に好ましい。
また、得られるパターン(硬化物)の膜強度の観点からは、本発明に係る樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6. More preferred are compounds having
Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition according to the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
芳香族多環構造を有するラジカル架橋剤としては、例えば、1,3-ジビニルナフタレン、アセナフチレン、9,9-ビス[4-[2-(アクリロイルオキシ)エトキシ]フェニル]-9H-フルオレン、9,9-ビス[4-[2-[2-(アクリロイルオキシ)エトキシ]エトキシ]フェニル]-9H-フルオレン、下記構造の化合物等が挙げられる。
Examples of radical cross-linking agents having an aromatic polycyclic structure include 1,3-divinylnaphthalene, acenaphthylene, 9,9-bis[4-[2-(acryloyloxy)ethoxy]phenyl]-9H-fluorene, 9, 9-bis[4-[2-[2-(acryloyloxy)ethoxy]ethoxy]phenyl]-9H-fluorene, compounds having the following structures, and the like.
具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、PEG(ポリエチレングリコール)200ジアクリレート、PEG200ジメタクリレート、PEG600ジアクリレート、PEG600ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、3-メチル-1,5-ペンタンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,6ヘキサンジオールジメタクリレート、ジメチロール-トリシクロデカンジアクリレート、ジメチロール-トリシクロデカンジメタクリレート、ビスフェノールAのEO(エチレンオキシド)付加物ジアクリレート、ビスフェノールAのEO付加物ジメタクリレート、ビスフェノールAのPO(プロピレンオキシド)付加物ジアクリレート、ビスフェノールAのPO付加物ジメタクリレート、2-ヒドロキシー3-アクリロイロキシプロピルメタクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する2官能アクリレート、ウレタン結合を有する2官能メタクリレートを使用することができる。これらは必要に応じ、2種以上を混合し使用することができる。
なお、例えばPEG200ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が200程度のものをいう。
本発明に係る樹脂組成物は、パターン(硬化物)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。
その他、2官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。 From the viewpoint of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate. methacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO ( Propylene oxide) adduct diacrylate, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, Bifunctional methacrylates with urethane bonds can be used. These can be used in combination of two or more as needed.
For example, PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
In the resin composition according to the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product). Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
本発明に係る樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明に係る樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 [Other cross-linking agents]
It is also preferable that the resin composition according to the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
Other cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the amino group-containing compound, a melamine-based crosslinking agent is a melamine-based crosslinking agent, a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent, and an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent. A cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition according to the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of cross-linking agents.
上記化合物が有するアルコキシメチル基又はアシルオキシメチル基は、炭素数2~5が好ましく、炭素数2又は3が好ましく、炭素数2がより好ましい。
上記化合物が有するアルコキシメチル基及びアシルオキシメチル基の総数は1~10が好ましく、より好ましくは2~8、特に好ましくは3~6である。
上記化合物の分子量は好ましくは1500以下であり、180~1200が好ましい。 As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine. can be given as structural examples.
The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
The molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
R101及びR102は、それぞれ独立に、一価の有機基を表し、互いに結合して環を形成してもよい。 R 100 represents an alkyl group or an acyl group.
R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
R105は各々独立にアルキル基又はアルケニル基を示し、a、b及びcは各々独立に1~3であり、dは0~4であり、eは0~3であり、fは0~3であり、a+dは5以下であり、b+eは4以下であり、c+fは4以下である。
酸の作用により分解し、アルカリ可溶性基を生じる基、酸の作用により脱離する基、-C(R4)2COOR5で表される基におけるR5については、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、-C(R01)(R02)(OR39)等を挙げることができる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~5のアルキル基がより好ましい。
上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
上記シクロアルキル基としては、炭素数3~12のシクロアルキル基が好ましく、炭素数3~8のシクロアルキル基がより好ましい。
上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
上記アリール基は炭素数6~30の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
上記アラルキル基としては、炭素数7~20のアラルキル基が好ましく、炭素数7~16のアラルキル基がより好ましい。
上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
上記アルケニル基は炭素数3~20のアルケニル基が好ましく、炭素数3~16のアルケニル基がより好ましい。
また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。 In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
For R 5 in the group represented by —C(R 4 ) 2 COOR 5 , a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
In the formula, R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. R 36 and R 37 may combine with each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The above alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms.
Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
耐熱性の観点で、アルコキシメチル基又はアシルオキシメチル基が、直接芳香環やトリアジン環上に置換した化合物が好ましい。 As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril;
urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based cross-linking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxymethyl ethylene urea;
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl propylene urea-based cross-linking agents such as propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which a seed group is directly attached are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 ,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3′,5,5′-tetrakis ( methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、本発明に係る樹脂組成物の低温硬化及び反りの抑制に効果的である。 - Epoxy compound (compound having an epoxy group) -
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the resin composition according to the present invention.
芳香族多環構造を有するエポキシ化合物としては、例えば、下記構造の化合物が挙げられる。
Examples of epoxy compounds having an aromatic polycyclic structure include compounds having the following structures.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。 -Oxetane compound (compound having an oxetanyl group)-
The oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (eg, OXT-121, OXT-221) can be suitably used, and these can be used alone or in combination of two or more. good.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 -Benzoxazine compound (compound having a benzoxazolyl group)-
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
本発明に係る樹脂組成物は、光及び/又は熱により重合を開始させることができる重合開始剤を含むことが好ましい。特に光重合開始剤を含むことが好ましい。
光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Polymerization initiator]
The resin composition according to the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す;
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R X3 to R X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R X10 to R X14 is an electron-withdrawing group.
なお、光重合開始剤は熱重合開始剤としても機能する場合があるため、オーブンやホットプレート等の加熱によって光重合開始剤による架橋を更に進行させられる場合がある。 When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition according to the present invention. Yes, more preferably 0.5 to 15% by mass, still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、べンゾピラン系、インジゴ系等の化合物を使用することができる。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン(7-(ジエチルアミノ)クマリン-3-カルボン酸エチル)、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンゾチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
また、他の増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Other sensitizing dyes may also be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.
本発明に係る樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内に-S-S-、-SO2-S-、-N-O-、SH、PH、SiH、及びGeHを有する化合物群、RAFT(Reversible Addition Fragmentation chain Transfer)重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The resin composition according to the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.
本発明に係る樹脂組成物は、熱重合開始剤を含むことも好ましい。
特に、第2の樹脂組成物が熱重合開始剤を含むことにより、例えば、上述の第2の前加熱工程、又は、上述の第2の後加熱工程において、重合性化合物の重合を促進することができる。
熱重合開始剤としては、重合性化合物の種類に応じて選択することができるが、熱ラジカル重合開始剤が好ましい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。
また、上述した光重合開始剤も熱により重合を開始する機能を有する場合があり、熱重合開始剤として添加することができる場合がある。 <Thermal polymerization initiator>
The resin composition according to the present invention preferably also contains a thermal polymerization initiator.
In particular, by including a thermal polymerization initiator in the second resin composition, for example, in the above second preheating step or the above second postheating step, the polymerization of the polymerizable compound can be promoted. can be done.
The thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound.
Moreover, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
熱重合開始剤としては、市販品を用いることもでき、富士フイルム和光純薬(株)製のV-40、V-601、VF-096、日油(株)製のパーへキシルO、パーへキシルD、パーへキシルI、パーヘキサ25O、パーヘキサ25Z、パークミルD、パークミルD-40、パークミルD-40MB、パークミルH、パークミルP、パークミルND等が挙げられる。
また、熱ラジカル重合開始剤として、具体的には、特開2008-063554号公報の段落0074~0118に記載されている化合物が挙げられ、この内容は本明細書に組み込まれる。 Examples of thermal polymerization initiators include known azo compounds and known peroxide compounds. Examples of azo-based compounds include azobis-based compounds. The azo compound may be a compound having a cyano group or a compound having no cyano group. Peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like.
As the thermal polymerization initiator, commercially available products can also be used, such as V-40, V-601 and VF-096 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Perhexyl O manufactured by NOF Corporation, Per Hexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percmyl D, Percmyl D-40, Percmyl D-40MB, Percmyl H, Percmyl P, Percmyl ND and the like.
Further, specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
樹脂組成物(特に、第2の樹脂組成物)は、熱重合開始剤を、1種単独で含んでいても、2種以上を含んでいてもよい。2種以上を含む場合、その合計量が上記範囲内となることが好ましい。 The content of the thermal polymerization initiator in the resin composition (especially the second resin composition) is preferably 0.05% by mass or more and 10% by mass or less with respect to the total solid content of the second resin composition. , more preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.
The resin composition (particularly, the second resin composition) may contain one type of thermal polymerization initiator alone, or two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
本発明に係る樹脂組成物は、光酸発生剤を含むことが好ましい。
光酸発生剤とは、200nm~900nmの光照射により、ブレンステッド酸、及び、ルイス酸の少なくとも一方を発生させる化合物を表す。照射される光は、好ましくは波長300nm~450nmの光であり、より好ましくは330nm~420nmの光である。光酸発生剤単独または増感剤との併用において、感光して酸を発生させることが可能な光酸発生剤であることが好ましい。
発生する酸の例としては、ハロゲン化水素、カルボン酸、スルホン酸、スルフィン酸、チオスルフィン酸、リン酸、リン酸モノエステル、リン酸ジエステル、ホウ素誘導体、リン誘導体、アンチモン誘導体、過酸化ハロゲン、スルホンアミド等が好ましく挙げられる。 [Photoacid generator]
The resin composition according to the present invention preferably contains a photoacid generator.
A photoacid generator is a compound that generates at least one of Bronsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photoacid generator is preferably a photoacid generator capable of generating an acid upon exposure.
Examples of generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
感度、保存安定性の観点から、有機ハロゲン化合物、オキシムスルホネート化合物、オニウム塩化合物が好ましく、形成する膜の機械特性等から、オキシムエステルが好ましい。 Examples of the photoacid generator used in the resin composition according to the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, onium salt compounds and the like.
Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のX3は同一でも異なっていてもよい。
式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシ基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシ基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 In formula (OS- 1 ), X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3's, they may be the same or different. The alkyl group and alkoxy group in X3 above may have a substituent. The alkyl group for X 3 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group for X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. As the halogen atom for X3 , a chlorine atom or a fluorine atom is preferable.
In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3 , multiple X3's may be the same or different.
In formula (OS-1), R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxy group of
式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and each R s2 , which may be present in plurality, is independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom, and each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. , ns represents 1 or 2, and ms represents an integer of 0-6.
In formulas (OS-103) to (OS-105), an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (preferably having 6 to 30 carbon atoms) represented by R s1 Numbers 4 to 30 are preferable) may have a known substituent as long as the effects of the present invention can be obtained.
式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。 In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group. Among R s2 that may be present in the compound at least two times, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. , one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5- or 6-membered ring.
式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。 In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
In formulas (OS-103) to (OS-105), an alkyl group (preferably having 1 to 30 carbon atoms) and an alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, the number of
In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the above oxime sulfonate compound, the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH2-、-CRu6H-又はCRu6Ru7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。 In formula (OS-101) or (OS-102), R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group. An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
In formula (OS-101) or (OS-102), R u2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、下記b-9、b-16、b-31、b-33が好ましい。
In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferred.
より好適には、すくなくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。 Specific examples of organic halogenated compounds include those described by Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Pat. 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 , JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P. P. Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), the contents of which are incorporated herein. Particularly preferred examples include an oxazole compound substituted with a trihalomethyl group: an S-triazine compound.
More preferably, s-triazine derivatives having at least one mono-, di-, or trihalogen-substituted methyl group attached to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)- s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) -2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4 ,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine , 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s- triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine and the like.
光酸発生剤は、1種単独で使用されても、複数種の組み合わせで使用されてもよい。複数種の組み合わせの場合には、それらの合計量が上記範囲にあることが好ましい。
また、所望の光源に対して、感光性を付与する為、増感剤と併用することも好ましい。 The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may be used in combination of multiple types. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
Moreover, in order to impart photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.
本発明に係る樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明に係る樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、2級アミン、3級アミンが挙げられる。
本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α-アミノアセトフェノン誘導体化合物、4級アンモニウム塩誘導体化合物、ピリジニウム塩、α-ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式(B1)、式(B2)、又は式(B3)で表される化合物が挙げられる。
The resin composition according to the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators for the resin composition according to the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the cured product has good mechanical properties and chemical resistance. Performance as an interlayer insulating film for wiring layers is improved.
The base generator may be an ionic base generator or a non-ionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like can be used.
Specific compounds of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb 13 is preferably an arylalkyl group.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
環状アルキル基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状アルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等が挙げられる。
鎖状アルキル基と環状アルキル基の組合せに係る基は、炭素数4~24のものが好ましく、4~18がより好ましく、4~12がさらに好ましい。鎖状アルキル基と環状アルキル基の組合せに係る基は、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基、シクロヘキシルプロピル基、メチルシクロヘキシルメチル基、エチルシクロヘキシルエチル基等が挙げられる。
酸素原子を鎖中に有するアルキル基は、炭素数2~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。酸素原子を鎖中に有するアルキル基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。
なかでも、後述する分解生成塩基の沸点を高める観点で、RN1およびRN2は炭素数5~12のアルキル基が好ましい。ただし、金属(例えば銅)の層と積層する際の密着性を重視する処方においては、環状のアルキル基を有する基や炭素数1~8のアルキル基であることが好ましい。 Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains. Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
Among them, from the viewpoint of raising the boiling point of the decomposition base described later, R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a prescription that emphasizes adhesion when laminating with a metal (eg, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
2価の炭化水素連結基は、炭素数1~24のものが好ましく、2~12がより好ましく、2~6がさらに好ましい。2価の脂肪族炭化水素基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。2価の芳香族炭化水素基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。2価の脂肪族炭化水素基と2価の芳香族炭化水素基の組み合わせに係る基(例えば、アリーレンアルキル基)は、炭素数7~22のものが好ましく、7~18がより好ましく、7~10がさらに好ましい。 The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred. These groups preferably have no oxygen atoms.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. A group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (eg, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
直鎖または分岐の鎖状アルキレン基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。
環状アルキレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。
鎖状アルキレン基と環状アルキレン基の組み合わせに係る基は、炭素数4~24のものが好ましく、4~12がより好ましく、4~6がさらに好ましい。
酸素原子を鎖中に有するアルキレン基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。酸素原子を鎖中に有するアルキレン基は、炭素数1~12のものが好ましく、1~6がより好ましく、1~3がさらに好ましい。 Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group and an arylenealkylene group are preferred.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
The group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
環状のアルケニレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状のアルケニレン基は、C=C結合の数は1~6が好ましく、1~4がより好ましく、1~2がさらに好ましい。
アリーレン基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。
アリーレンアルキレン基は、炭素数7~23のものが好ましく、7~19がより好ましく、7~11がさらに好ましい。
中でも、鎖状アルキレン基、環状アルキレン基、酸素原子を鎖中に有するアルキレン基、鎖状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましく、1,2-エチレン基、プロパンジイル基(特に1,3-プロパンジイル基)、シクロヘキサンジイル基(特に1,2-シクロヘキサンジイル基)、ビニレン基(特にシスビニレン基)、フェニレン基(1,2-フェニレン基)、フェニレンメチレン基(特に1,2-フェニレンメチレン基)、エチレンオキシエチレン基(特に1,2-エチレンオキシ-1,2-エチレン基)がより好ましい。 The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C═C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
塩基発生剤は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the resin composition according to the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition according to the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
One or two or more base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.
本発明に係る樹脂組成物は、溶剤を含むことが好ましい。
溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition according to the present invention preferably contains a solvent.
Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
本発明に係る樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等が挙げられる。 <Metal adhesion improver>
The resin composition according to the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-ketoesters. compounds, amino compounds, and the like.
シランカップリング剤としては、例えば、国際公開第2015/199219号の段落0167に記載の化合物、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開第2011/080992号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-041264号公報の段落0045~0052に記載の化合物、国際公開第2014/097594号の段落0055に記載の化合物、特開2018-173573の段落0067~0078に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Meはメチル基を、Etはエチル基を表す。 〔Silane coupling agent〕
Examples of the silane coupling agent include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum Adhesion Aid]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
本発明に係る樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition according to the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
本発明に係る樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、N-オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。 <Polymerization inhibitor>
The resin composition according to the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
本発明に係る樹脂組成物は、露光から加熱までの経時による性能変化を低減するために、酸捕捉剤を含有することが好ましい。ここで酸捕捉剤とは、系中に存在することで発生酸を捕捉することができる化合物を指し、酸性度が低くpKaの高い化合物であることが好ましい。酸捕捉剤としては、アミノ基を有する化合物が好ましく、1級アミン、2級アミン、3級アミン、アンモニウム塩、3級アミドなどが好ましく、1級アミン、2級アミン、3級アミン、アンモニウム塩が好ましく、2級アミン、3級アミン、アンモニウム塩がより好ましい。
酸捕捉剤としては、イミダゾール構造、ジアザビシクロ構造、オニウム構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び/又はエーテル結合を有するアルキルアミン誘導体、水酸基及び/又はエーテル結合を有するアニリン誘導体等を好ましく挙げることができる。オニウム構造を有する場合、酸捕捉剤はアンモニウム、ジアゾニウム、ヨードニウム、スルホニウム、ホスホニウム、ピリジニウムなどから選択されるカチオンと、酸発生剤が発生する酸より酸性度の低い酸のアニオンとを有する塩であることが好ましい。 <Acid Scavenger>
The resin composition according to the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa. The acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
Examples of acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
本発明に係る組成物は、酸捕捉剤を含有してもしなくてもよいが、含有する場合、酸捕捉剤の含有量は、組成物の全固形分を基準として、通常は0.001~10質量%であり、好ましくは0.01~5質量%である。 These acid scavengers may be used singly or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually from 0.001 to 0.001 based on the total solid content of the composition. 10% by mass, preferably 0.01 to 5% by mass.
本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、界面活性剤、高級脂肪酸誘導体、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類(例えば、消泡剤、難燃剤など)等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
The resin composition of the present invention may optionally contain various additives such as surfactants, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organic titanium compounds, oxide Inhibitors, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (eg, antifoaming agents, flame retardants, etc.), etc., can be added. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、炭化水素系界面活性剤などの各種界面活性剤を使用できる。界面活性剤はノニオン型界面活性剤であってもよく、カチオン型界面活性剤であってもよく、アニオン型界面活性剤であってもよい。 [Surfactant]
As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、市販品としては、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。 The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
A fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein. Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
界面活性剤の含有量は、組成物の全固形分に対して、0.001~2.0質量%が好ましく、0.005~1.0質量%がより好ましい。 Only one type of surfactant may be used, or two or more types may be used in combination.
The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
本発明に係る樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で本発明に係る樹脂組成物の表面に偏在させてもよい。 [Higher Fatty Acid Derivative]
In the resin composition according to the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. It may be unevenly distributed on the surface of the composition.
本発明に係る樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
The resin composition according to the present invention may contain inorganic particles. Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
無機粒子の上記平均粒子径は、一次粒子径であり、また体積平均粒子径である。体積平均粒子径は、Nanotrac WAVE II EX-150(日機装社製)による動的光散乱法で測定できる。
上記測定が困難である場合は、遠心沈降光透過法、X線透過法、レーザー回折・散乱法で測定することもできる。 The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferred.
The average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, the above various ultraviolet absorbers may be used singly or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of this embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds.
Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。上述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. A substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, as the antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein. The composition of the present invention may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
本実施形態の樹脂組成物は、必要に応じて凝集防止剤を含有してもよい。凝集防止剤としては、ポリアクリル酸ナトリウム等が挙げられる。 [Anti-aggregation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Anti-aggregation agents include sodium polyacrylate and the like.
本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上10質量%以下であることが好ましく、0.02質量%以上5質量%以下であることがより好ましい。 In the present invention, the aggregation inhibitor may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
本実施形態の樹脂組成物は、必要に応じてフェノール系化合物を含有してもよい。フェノール系化合物としては、Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、メチレントリス-FR-CR、BisRS-26X(以上、商品名、本州化学工業(株)製)、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F(以上、商品名、旭有機材工業(株)製)等が挙げられる。 [Phenolic compound]
The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
他の高分子化合物としては、シロキサン樹脂、(メタ)アクリル酸を共重合した(メタ)アクリルポリマー、ノボラック樹脂、レゾール樹脂、ポリヒドロキシスチレン樹脂およびそれらの共重合体などが挙げられる。他の高分子化合物はメチロール基、アルコキシメチル基、エポキシ基などの架橋基が導入された変性体であってもよい。 [Other polymer compounds]
Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, other polymer compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds, but if it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
本発明に係る樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、1,000mm2/s~12,000mm2/sが好ましく、2,000mm2/s~10,000mm2/sがより好ましく、2,500mm2/s~8,000mm2/sが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。1,000mm2/s以上であれば、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが容易であり、12,000mm2/s以下であれば、塗布面状に優れた塗膜が得られる。 <Characteristics of resin composition>
The viscosity of the resin composition according to the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
本発明に係る樹脂組成物の含水率は、2.0質量%未満であることが好ましく、1.5質量%未満であることがより好ましく、1.0質量%未満であることが更に好ましい。2.0%未満であれば、樹脂組成物の保存安定性が向上する。
水分の含有量を維持する方法としては、保管条件における湿度の調整、保管時の収容容器の空隙率低減などが挙げられる。 <Restrictions on Substances Contained in Resin Composition>
The water content of the resin composition according to the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the resin composition according to the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, more preferably less than 300 ppm by mass, and 200 ppm by mass from the viewpoint of wiring corrosion resistance. Less than is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
冷却管と撹拌装置を装着したセパラブルフラスコに、2,4-ジメチルフェノール49g(0.4モル)、m-クレゾール173g(1.6モル)、37質量%ホルムアルデヒド水溶液130g(1.6モル)、シュウ酸2水和物12.6g(0.1モル)およびメチルイソブチルケトン550gを仕込み、90~100℃の温度に保持し撹拌しながら8時間反応させた。この溶液をイオン交換水500gで2回水洗した後、n-ヘキサン600gを加え、30分間撹拌し、1時間静置した。その後、析出した樹脂層の上澄み液をデカンデーションによって取り除いた。得られた樹脂層を濃縮し、脱水し、乾燥し、Mw8000の樹脂(ポリマーP-1)を得た。 <Synthesis Example 1; Synthesis of Polymer P-1>
49 g (0.4 mol) of 2,4-dimethylphenol, 173 g (1.6 mol) of m-cresol, and 130 g (1.6 mol) of 37% by mass aqueous formaldehyde solution were placed in a separable flask equipped with a condenser and a stirrer. , 12.6 g (0.1 mol) of oxalic acid dihydrate and 550 g of methyl isobutyl ketone were charged and reacted for 8 hours while maintaining the temperature at 90 to 100° C. and stirring. After washing this solution twice with 500 g of ion-exchanged water, 600 g of n-hexane was added, stirred for 30 minutes, and allowed to stand for 1 hour. After that, the supernatant liquid of the deposited resin layer was removed by decantation. The resulting resin layer was concentrated, dehydrated and dried to obtain a resin (Polymer P-1) of Mw 8000.
4,4’-オキシジフタル酸二無水物(ODPA)7.76g(25ミリモル)および3,3’,4,4’-ビフェニルテトラカルボン酸二無水物6.23g(25ミリモル)を反応容器に入れ、2-ヒドロキシエチルメタクリレート(HEMA)13.4g及びγ―ブチロラクトン100mlを加えた。室温下で撹拌しながら、ピリジン7.91gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。
次に、氷冷下において、反応混合物に、ジシクロヘキシルカルボジイミド(DCC)20.6g(99.9ミリモル)をγ-ブチロラクトン30mlに溶解した溶液を、撹拌しながら40分かけて加えた。続いて、4,4’-ジアミノジフェニルエーテル(DADPE)9.3g(46ミリモル)をγ-ブチロラクトン350mlに懸濁した懸濁液を、攪拌しながら60分かけて加えた。
更に室温で2時間撹拌した後、エチルアルコール3mlを加えて1時間撹拌した。その後、γ-ブチロラクトン100mlを加えた。反応混合物に生じた沈殿物を、ろ過により取り除き、反応液を得た。
得られた反応液を3リットルのエチルアルコールに加えて、粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾取し、テトラヒドロフラン200mlに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を3リットルの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾取した後に真空乾燥することにより、粉末状のポリマーP-2を得た。
このポリマーの重量平均分子量(Mw)を測定したところ、23,000であった。
ポリマーP-2は下記構造の樹脂である。括弧の添字は各繰り返し単位のモル比を表す。
7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were placed in a reaction vessel. , 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 7.91 g of pyridine while stirring at room temperature. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand still for 16 hours.
Next, under ice-cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring.
After further stirring at room temperature for 2 hours, 3 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. 100 ml of γ-butyrolactone was then added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The resulting crude polymer was collected by filtration and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 3 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer P-2.
The weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
Polymer P-2 is a resin having the following structure. Subscripts in parentheses represent the molar ratio of each repeating unit.
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を冷却し、16.12g(135.5ミリモル)のSOCl2を2時間かけて加えた。次いで、100mLのN-メチルピロリドンに11.32g(60.0ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-5~0℃の温度範囲に調整しつつ、2時間かけて反応混合物に滴下した。反応混合物を0℃で1時間反応させたのち、エタノールを70g加えて、室温で1時間撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpmの速度で15分間撹拌した。ポリイミド前駆体をろ過して除き、4リットルの水の中で再度30分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、2日間乾燥した。このポリイミド前駆体(ポリマーP-3)の重量平均分子量は、29,000であった。
ポリマーP-3は下記構造の樹脂である。
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . The reaction mixture was then cooled and 16.12 g (135.5 mmol) of SOCl 2 was added over 2 hours. Then, a solution of 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added over 2 hours while adjusting the temperature to -5 to 0°C. It was added dropwise to the reaction mixture. After reacting the reaction mixture at 0° C. for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure for two days. The weight average molecular weight of this polyimide precursor (polymer P-3) was 29,000.
Polymer P-3 is a resin having the following structure.
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例3と同様にN-メチルピロリドンに4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、反応混合物に滴下し、その後得た反応混合物を精製、乾燥した。このポリイミド前駆体(ポリマーP-4)の重量平均分子量は、18,000であった。
ポリマーP-4は下記構造の樹脂である。
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Then, after chlorinating the obtained diester with SOCl 2 , a solution of 4,4'-diaminodiphenyl ether dissolved in N-methylpyrrolidone was added dropwise to the reaction mixture in the same manner as in Synthesis Example 3, and then the resulting reaction The mixture was purified and dried. The weight average molecular weight of this polyimide precursor (polymer P-4) was 18,000.
Polymer P-4 is a resin having the following structure.
乾燥窒素気流下、4,4’-ジカルボキシジフェニルエーテルと1-ヒドロキシベンゾトリアゾールからなるジカルボン酸ジエステル88.64g(180ミリモル)、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン65.93g(180ミリモル)、ED-600(商品名、HUNTSMAN(株)製)12.00g(20ミリモル)、NMP800gを25℃で30分反応させ、次いでオイルバスで加熱し、80℃で8時間反応させた。次に末端封止剤として5-ノルボルネン-2,3-ジカルボン酸無水物12.31g(75ミリモル)を加え、80℃でさらに3時間攪拌して反応を終了した。反応終了後、溶液を室温まで冷却した後、反応混合物を濾過し、反応混合物を、水/イソプロパノール=3/1(体積比)の混合液2Lに投入して沈殿物を得た。この沈殿物を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で20時間乾燥し、ポリマーP-5(ポリベンゾオキサゾール前駆体)を得た。重量平均分子量は28,000であった。 <Synthesis Example 5; Synthesis of Polymer P-5>
Under dry nitrogen stream, 88.64 g (180 mmol) of dicarboxylic acid diester composed of 4,4′-dicarboxydiphenyl ether and 1-hydroxybenzotriazole, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 65.93 g (180 mmol), 12.00 g (20 mmol) of ED-600 (trade name, manufactured by HUNTSMAN Co., Ltd.), and 800 g of NMP were reacted at 25°C for 30 minutes, then heated in an oil bath and heated to 80°C for 8 hours. reacted over time. Next, 12.31 g (75 millimoles) of 5-norbornene-2,3-dicarboxylic anhydride was added as a terminal blocking agent, and the mixture was stirred at 80°C for 3 hours to complete the reaction. After completion of the reaction, the solution was cooled to room temperature, the reaction mixture was filtered, and the reaction mixture was added to 2 L of a mixed liquid of water/isopropanol=3/1 (volume ratio) to obtain a precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 20 hours to obtain polymer P-5 (polybenzoxazole precursor). The weight average molecular weight was 28,000.
具体的には、表に記載の成分の含有量は、表に記載の量(質量部)とした。また、表中、「-」の記載は該当する成分を組成物が含有していないことを示している。 Each composition was obtained by mixing the components shown in the table below.
Specifically, the contents of the components described in the table were the amounts (parts by mass) described in the table. In the table, the description of "-" indicates that the composition does not contain the corresponding component.
〔樹脂〕
・P-1~P-5:上記で合成したP-1~P-5
・P-6:エポキシ樹脂(EPICION N-690,DIC製) Details of the abbreviations in the table are as follows.
〔resin〕
· P-1 to P-5: P-1 to P-5 synthesized above
・ P-6: Epoxy resin (EPICION N-690, manufactured by DIC)
・B-1:新中村化学工業(株)製、ポリエチレングリコール#200ジメタクリレート(4G)
・B-2:新中村化学工業(株)製、A-TMMT
・B-3:ヘキサメトキシメチルメラミン
・B-4:TML-BPA(本州化学工業(株)製)
・B-5:セロキサイド2021P((株)ダイセル製)
・B-6:テトラエチレングリコールジメタクリレート
・B-7:EX-321L(ナガセケムテックス社製)
・B-8:エチレングリコールジメタクリレート(東京化成工業社製)
・B-9:下記構造の化合物
・B-10:下記構造の化合物
· B-1: manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 200 dimethacrylate (4G)
・ B-2: Shin-Nakamura Chemical Co., Ltd., A-TMMT
・B-3: Hexamethoxymethyl melamine ・B-4: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.)
・ B-5: Celoxide 2021P (manufactured by Daicel Co., Ltd.)
・B-6: Tetraethylene glycol dimethacrylate ・B-7: EX-321L (manufactured by Nagase ChemteX Corporation)
· B-8: ethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・B-9: A compound having the following structure ・B-10: A compound having the following structure
・C-1:Irgacure OXE-01(BASF社製)
・C-2:Irgacure OXE-02(BASF社製)
・C-3:Irgacure 784(BASF社製)
・C-4:CPI-210S(サンアプロ(株)製)
・C-5:Lambson社製G-1820
・C-6:TrisP-PA(α,α,α’-トリス(4-ヒドロキシフェニル)-1-エチル-4-イソプロピルベンゼン)のヒドロキシ基を1,2-ナフトキノン-2-ジアジド-4-スルホニルクロリドを用いてジアゾナフトキノン化した化合物
・C-7:1-フェニル-2-[(ベンゾイルオキシ)イミノ]-1-プロパノン
・C-8:2,2’-アゾジイソブチロニトリル(東京化成工業社製)
・C-9:パーヘキサ25Z(日油社製)
・C-10:パークミルD(日油社製) [Polymerization initiator]
・ C-1: Irgacure OXE-01 (manufactured by BASF)
・ C-2: Irgacure OXE-02 (manufactured by BASF)
・ C-3: Irgacure 784 (manufactured by BASF)
・ C-4: CPI-210S (manufactured by San-Apro Co., Ltd.)
・ C-5: G-1820 manufactured by Lambson
· C-6: 1,2-naphthoquinone-2-diazide-4-sulfonyl for the hydroxy group of TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene) Compound diazonaphthoquinone using chloride C-7: 1-phenyl-2-[(benzoyloxy)imino]-1-propanone C-8: 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd. made)
・ C-9: Perhexa 25Z (manufactured by NOF Corporation)
・ C-10: Parkmill D (manufactured by NOF Corporation)
・D-1:KBM-403(3-グリシドキシプロピルトリメトキシシラン)(信越シリコーン(株)製)
・D-2:γウレイドプロピルトリエチルシラン
・D-3:N-[3-(トリエトキシシリル)プロピル]マレインアミド酸
・D-4:N-(3-トリエトキシシリル)プロピル)-フタルアミド酸
・D-5:KBM-502(3-メタクリロキシプロピルメチルジメトキシシラン)(信越シリコーン(株)製) [Metal adhesion improver]
・ D-1: KBM-403 (3-glycidoxypropyltrimethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.)
・D-2: γ-ureidopropyltriethylsilane ・D-3: N-[3-(triethoxysilyl)propyl]maleamic acid ・D-4: N-(3-triethoxysilyl)propyl)-phthalamic acid ・D-5: KBM-502 (3-methacryloxypropylmethyldimethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.)
・E-1:5-アミノテトラゾール [Migration inhibitor]
・ E-1: 5-aminotetrazole
・F-1:2MeHQ(メトキシヒドロキノン)
・F-2:TAOBN(1,4,4-トリメチル-2,3-ジアザビシクロ[3.2.2]-ノナ-2-エン-N,N-ジクソイド)
・F-3:4MeHQ(4-メトキシフェノール)
・F-4:PBQ(p-ベンゾキノン) [Polymerization inhibitor]
・ F-1: 2MeHQ (methoxyhydroquinone)
・ F-2: TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dixoid)
・ F-3: 4MeHQ (4-methoxyphenol)
・ F-4: PBQ (p-benzoquinone)
・G-1:メガファックF444(DIC(株)製)
・G-2:メガファックF470(DIC(株)製) [Surfactant]
・G-1: Megaface F444 (manufactured by DIC Corporation)
・G-2: Megafac F470 (manufactured by DIC Corporation)
・H-1:1-[4-(2-ヒドロキシエチル)-1-ピペリジニル]-3-(2-ヒドロキシフェニル)-1-プロパノン [Base generator]
· H-1: 1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone
・I-1:下記構造の化合物
・I-2:下記構造の化合物、Etはエチル基を表す。
・I-3:N-フェニルジエタノールアミン
・I-4:下記構造の化合物
・I-5:TrisP-PA(α,α,α’-トリス(4-ヒドロキシフェニル)-1-エチル-4-イソプロピルベンゼン)
• I-1: compound having the following structure • I-2: compound having the following structure, Et represents an ethyl group.
・I-3: N-phenyldiethanolamine ・I-4: A compound having the following structure ・I-5: TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene )
・J-1:GBL(γ-ブチロラクトン)
・J-2:DMSO(ジメチルスルホキシド)
・J-3:EL(乳酸エチル)
・J-4:NMP(N-メチル-2-ピロリドン)
・J-5:CP(シクロペンタノン) 〔solvent〕
・ J-1: GBL (γ-butyrolactone)
・ J-2: DMSO (dimethyl sulfoxide)
・ J-3: EL (ethyl lactate)
・ J-4: NMP (N-methyl-2-pyrrolidone)
・ J-5: CP (cyclopentanone)
<複合パターンの作製>
各実施例において、表に記載の第1の組成物をシリコンウエハ上にスピンコート法により適用し、ホットプレート上で、100℃で5分間乾燥して、表に記載の膜厚の塗膜を形成した。その後表に記載の各処理(処理1~処理5、ただし、「-」と記載の欄については、何らの処理も行っていないことを示している)を実施した。 (evaluation)
<Preparation of Composite Pattern>
In each example, the first composition listed in the table was applied by spin coating onto a silicon wafer and dried on a hot plate at 100°C for 5 minutes to form a coating film having the thickness listed in the table. formed. After that, each treatment described in the table (
第1の組成物はスピンコート後、処理1として表に記載の条件で加熱(処理1)し、表に記載の膜厚の塗膜を形成した。その後得られた塗膜上に処理2として、組成物8を塗布し、5μmの塗膜を形成した。処理3としてi線露光機を用いマスクを介して凹パターン(抜き)を露光した。処理4として2.38質量%TMAH(テトラメチルアンモニウムヒドロキシド)水溶液で60秒現像を実施した。処理5として得られた組成物8のパターンをマスクにドライエッチを行い、第1の組成物のパターンを得た。第2の組成物を先の工程を経て形成された第1の組成物のパターン上に更に塗布した。第2の組成物の処理1を実施後、処理2の現像を実施し、複合パターンを得た。 <Example 1>
After spin coating, the first composition was heated under the conditions shown in the table as treatment 1 (treatment 1) to form a coating film having the thickness shown in the table. As
第1の組成物はスピンコート後、処理1としてi線露光機を用いマスクを介して凹パターン(抜き)を露光。処理2として2.38質量%TMAH水溶液で60秒現像を実施した。処理3として表に記載の条件で後加熱を実施し、第1の組成物のパターンを得た。第2の組成物を先の工程を経て形成された第1の組成物のパターン上に更に塗布した。第2の組成物の処理1を実施後、処理2の現像を実施し、複合パターンを得た。 <Example 2>
After the first composition was spin-coated, as
第1の組成物はスピンコート後、処理1としてi線露光機を用いマスクを介して凹パターン(抜き)を露光した。処理2としてPGMEA(プロピレングリコールモノメチルエーテルアセテート)で60秒現像を実施した。処理3として後加熱を実施し、第1の組成物のパターンを得た。第2の組成物を先の工程を経て形成された第1の組成物のパターン上に更に塗布した。第2の組成物の処理1を実施後、処理2の現像を実施し、複合パターンを得た。 <Example 3>
After the first composition was spin-coated, as
第1の組成物はスピンコート後、処理1としてi線露光機を用いマスクを介して凹パターン(抜き)を露光した。処理2としてシクロペンタノンで60秒現像を実施した。処理3として後加熱を実施し、第1の組成物のパターンを得た。第2の組成物を先の工程を経て形成された第1の組成物のパターン上に更に塗布した。第2の組成物の処理1を実施後、処理2の現像を実施し、処理3の加熱を経て、複合パターンを得た。
但し、実施例11の第2の組成物の処理2は前記実施例3記載の処理を行った。 <Example 4-17>
After the first composition was spin-coated, as
However, in the
第1の組成物のパターン形成後に断面SEM(走査型電子顕微鏡による断面観察)を用いて第1の組成物のパターンにおけるトップのパターン幅を測定した。そのパターン幅をD1とした。
第2の組成物のすべての処理後の複合パターンのパターン幅をD2とし、D2-D1が0.5μm以上の場合を“判定A”とし、0.2μm以上で0.5μm未満の場合を“判定B”とし、0.2μm未満の場合を“判定C”とした。評価結果は下記表の「シュリンク判定」の欄に記載した。D2-D1が大きいほど、微細なパターンを形成することができるといえる。 <Determination of Pattern Shrink>
After pattern formation of the first composition, the top pattern width of the pattern of the first composition was measured using a cross-sectional SEM (cross-sectional observation with a scanning electron microscope). The pattern width was set to D1.
The pattern width of the composite pattern after all the treatments of the second composition is D2, the case where D2-D1 is 0.5 μm or more is “determination A”, and the case where it is 0.2 μm or more and less than 0.5 μm is “ A case of less than 0.2 μm was judged to be “judgment B”, and a case of less than 0.2 μm was judged to be “judgment C”. The evaluation results are shown in the "shrink evaluation" column of the table below. It can be said that the larger D2−D1 is, the finer the pattern can be formed.
シリコンウエハを、10μmLS(ラインアンドスペース)の銅パターンを持つ基材に変更した以外は、上述の実施例1~17と同様の方法により、銅パターン上に複合パターンを付与した。その基材を175℃のオーブンに入れ、500時間保持した。その後、オーブンから基材を取り出し、イオンミリング装置を用いて断面切断し、SEM(走査型電子顕微鏡)にて断面観察を行った。銅―樹脂膜間で剥離が無い場合を“判定A”とし、銅-樹脂膜面における剥離部分の割合が0%超20%未満であった場合を“判定B”、銅-樹脂膜面における剥離部分の割合が20%超であった場合を“判定C”とした。評価結果は下記表の「HTS後の剥がれの有無」の欄に記載した。HTSとはHigh Temperature Storage Testを意味し、剥離が少ないほど信頼性試験後の密着性に優れる、すなわち、長期間において剥離を生じにくいといえる。 <Determination of Reliability Evaluation>
A composite pattern was applied to the copper pattern in the same manner as in Examples 1 to 17 above, except that the silicon wafer was changed to a substrate having a 10 μm LS (line and space) copper pattern. The substrate was placed in an oven at 175°C and held for 500 hours. After that, the substrate was taken out from the oven, cross-sectionally cut using an ion milling device, and cross-sectionally observed with a SEM (scanning electron microscope). The case where there is no peeling between the copper and the resin film is "judgment A", and the case where the ratio of the peeled portion on the copper-resin film surface is more than 0% and less than 20% is "judgment B", and the copper-resin film surface "Determination C" was given when the ratio of the peeled portion was more than 20%. The evaluation results are described in the column of "presence or absence of peeling after HTS" in the table below. HTS means High Temperature Storage Test, and it can be said that the less peeling, the better the adhesion after the reliability test, that is, the less peeling occurs over a long period of time.
シリコンウェハを、酸化銅膜を持つ8インチウエハに変更した以外は、上述の実施例1~17と同様の方法により、酸化銅膜上に複合パターンを付与した。i線露光時には、フォトマスクとして30×40mmのパターンを形成可能なものを使用した。第二の組成物に対する、上記表に記載の全ての処理が完了した後、徐冷した後、2N(2mol/L)-塩酸に2時間浸漬することで、ウエハから樹脂組成物の膜を剥がし、水洗後、実施例1~17の複合パターンの30x4mmの短冊状の膜を得た。引っ張り測定機INSTRON5965(インストロン社製)を用いて、室温23.0℃下で引張速度5mm/分で引っ張り、破断点伸度の測定を行なった。測定は1検体につき6枚の短冊について行ない、結果から上位3点の平均値を求めた。破断点伸度の値が40%以上のものを“判定A”とし、39%~10%のものを“判定B”とし、9%以下のものを“判定C”とした。評価結果は下記表の「破断伸び」の欄に記載した。破断点伸度が大きいほど膜強度に優れるといえる。 <Measurement of breaking elongation>
A composite pattern was formed on the copper oxide film in the same manner as in Examples 1 to 17 above, except that the silicon wafer was changed to an 8-inch wafer having a copper oxide film. At the time of i-line exposure, a photomask capable of forming a pattern of 30×40 mm was used. After all the treatments described in the above table for the second composition are completed, the wafer is slowly cooled and then immersed in 2N (2 mol/L)-hydrochloric acid for 2 hours to peel off the film of the resin composition from the wafer. , and after washing with water, 30 x 4 mm strip-shaped membranes of the composite patterns of Examples 1-17 were obtained. Using a tensile tester INSTRON 5965 (manufactured by Instron), the film was pulled at a tensile rate of 5 mm/min at room temperature of 23.0° C. to measure the elongation at break. Six strips were measured for each sample, and the average value of the top three points was obtained from the results. A sample with an elongation at break value of 40% or more was rated as "Judgement A", a value of 39% to 10% was rated as "Judgement B", and a value of 9% or less was rated as "Judgement C". The evaluation results are shown in the "elongation at break" column in the table below. It can be said that the higher the elongation at break, the better the film strength.
2 第1のパターン
4 パターン間の領域
6 第2の樹脂組成物の被膜
8 第2の樹脂組成物の被膜の除去される領域
10 第2のパターン
12 複合パターンのパターン間の領域 1
Claims (16)
- 第1の樹脂組成物を用いて、第1の樹脂組成物膜を基材上に形成し、第1のパターンを有する基材を得る工程、
前記第1のパターンを有する基材上に、第2の樹脂組成物を付与し、第1のパターン上、及び、第1のパターンの間の領域に第2の樹脂組成物の被膜を形成する工程、及び、
第2の樹脂組成物の被膜の一部を除去し、第1のパターンと接する第2のパターンを形成する工程を含み、
前記第1のパターンにおけるパターンの間の領域よりも、前記第1のパターン及び前記第2のパターンからなる複合パターンにおけるパターンの間の領域の方が狭い、
永久膜の製造方法。 A step of forming a first resin composition film on a substrate using a first resin composition to obtain a substrate having a first pattern;
A second resin composition is applied onto the substrate having the first pattern to form a coating of the second resin composition on the first pattern and on the region between the first patterns. process, and
removing a portion of the coating of the second resin composition to form a second pattern in contact with the first pattern;
an area between patterns in a composite pattern consisting of the first pattern and the second pattern is narrower than an area between patterns in the first pattern;
A method for manufacturing a permanent membrane. - 前記第1の樹脂組成物がネガ型感放射線性樹脂組成物である、請求項1に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 1, wherein the first resin composition is a negative radiation-sensitive resin composition.
- 前記第1のパターンを有する基材を得る工程が、前記第1の樹脂組成物膜を選択的に露光した後に、溶剤現像により現像する工程である、請求項1又は2に記載の永久膜の製造方法。 3. The permanent film according to claim 1 or 2, wherein the step of obtaining a substrate having the first pattern is a step of selectively exposing the first resin composition film and then developing it by solvent development. Production method.
- 前記第2のパターンを形成する工程が、前記第2の樹脂組成物の被膜の一部を溶剤現像により除去する工程である、請求項1~3のいずれか1項に記載の永久膜の製造方法。 Manufacture of the permanent film according to any one of claims 1 to 3, wherein the step of forming the second pattern is a step of removing part of the coating of the second resin composition by solvent development. Method.
- 前記第2の樹脂組成物の被膜を形成する工程の後、前記第2のパターンを形成する工程の前に、前記第1のパターン及び前記第2の樹脂組成物の被膜を加熱する工程を更に含む、請求項1~4のいずれか1項に記載の永久膜の製造方法。 After the step of forming the coating of the second resin composition and before the step of forming the second pattern, the step of heating the first pattern and the coating of the second resin composition is further provided. A method for producing a permanent film according to any one of claims 1 to 4, comprising:
- 前記第2の樹脂組成物が、熱重合開始剤を含む、請求項1~5のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 5, wherein the second resin composition contains a thermal polymerization initiator.
- 前記第2の樹脂組成物が、重合性基を有する樹脂を含む、請求項1~6のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 6, wherein the second resin composition contains a resin having a polymerizable group.
- 前記第2の樹脂組成物が、重合性基及びフルオレン骨格を有する化合物を含む、請求項1~7のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 7, wherein the second resin composition contains a compound having a polymerizable group and a fluorene skeleton.
- 前記第1の樹脂組成物に含まれる樹脂が、ポリイミド前駆体又はポリベンゾオキサゾール前駆体である、請求項1~8のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 8, wherein the resin contained in the first resin composition is a polyimide precursor or a polybenzoxazole precursor.
- 前記第2の樹脂組成物に含まれる樹脂が、ポリイミド前駆体又はポリベンゾオキサゾール前駆体である、請求項1~9のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 9, wherein the resin contained in the second resin composition is a polyimide precursor or a polybenzoxazole precursor.
- 得られる永久膜が、ポリイミド又はポリベンゾオキサゾールを含む、請求項1~10のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 10, wherein the obtained permanent film contains polyimide or polybenzoxazole.
- 前記第2のパターンを形成する工程の後に、加熱工程を更に含む、請求項1~11のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 11, further comprising a heating step after the step of forming the second pattern.
- 前記複合パターンの破断伸びが、40%以上である、請求項1~12のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 12, wherein the composite pattern has a breaking elongation of 40% or more.
- 前記第1のパターンが、ホールパターン及びトレンチパターンの少なくとも一方を含む、請求項1~13のいずれか1項に記載の永久膜の製造方法。 The method for producing a permanent film according to any one of claims 1 to 13, wherein the first pattern includes at least one of a hole pattern and a trench pattern.
- 請求項1~14のいずれか1項に記載の永久膜の製造方法を含む、積層体の製造方法。 A method for manufacturing a laminate, including the method for manufacturing the permanent film according to any one of claims 1 to 14.
- 請求項1~14のいずれか1項に記載の永久膜の製造方法、又は、請求項15に記載の積層体の製造方法を含む、半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, including the method for manufacturing the permanent film according to any one of claims 1 to 14 or the method for manufacturing the laminate according to claim 15.
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JP2012168503A (en) * | 2010-10-01 | 2012-09-06 | Fujifilm Corp | Gap embedding composition, method for embedding gap and method for manufacturing semiconductor device by using the composition |
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