WO2022045059A1 - 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス - Google Patents
樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス Download PDFInfo
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- WO2022045059A1 WO2022045059A1 PCT/JP2021/030783 JP2021030783W WO2022045059A1 WO 2022045059 A1 WO2022045059 A1 WO 2022045059A1 JP 2021030783 W JP2021030783 W JP 2021030783W WO 2022045059 A1 WO2022045059 A1 WO 2022045059A1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.
- Polyimide is applied to various applications because it has excellent heat resistance and insulating properties.
- the application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.
- polyimide is used in the form of a resin composition containing a polyamic acid ester.
- a resin composition is applied to a base material by, for example, coating to form a resin film, and then exposed, developed, heated or the like, if necessary, to form a cured product on the base material. be able to.
- the polyamic acid ester is, for example, cyclized by heating to become polyimide in a cured product. Since the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition at the time of application. It can be said that it is excellent in sex.
- the industrial application development of the above-mentioned resin composition is expected more and more.
- Patent Document 1 has (a) a polyimide and / or a polyimide precursor, (b) a photosensitizer, (c) high dielectric constant inorganic particles, (d) a solvent, and (c) high dielectric constant inorganic particles.
- a perovskite-type crystal structure or a composite perovskite-type crystal structure having one kind of average particle size, or one having two or more kinds of average particle sizes, and the minimum average particle size thereof is 0.06 ⁇ m.
- a photosensitive resin composition characterized by having the above-mentioned perovskite-type crystal structure or composite perovskite-type crystal structure is described.
- Patent Document 2 describes only from (A) a phosphorus compound having a specific structure, (B) a polyamic acid soluble in an organic solvent and / or a polyimide soluble in an organic solvent, and (C) C, H, O, and N atoms.
- a photosensitive resin composition is described in which different compounds are used and one or more (meth) acrylate compounds are contained.
- a cured product having excellent chemical resistance can be obtained, a resin composition having excellent storage stability, a cured product obtained by curing the resin composition, a laminate containing the cured product, and the production of the cured product. It is an object of the present invention to provide a method and a semiconductor device containing the cured product or the laminate.
- a 1 and A 2 represent an oxygen atom or -NH-
- R 113 and R 114 independently represent a monovalent organic group
- R 115 represents a tetravalent organic group.
- R 111 represents a divalent organic group.
- At least one of R 3 is a monovalent organic group having 1 to 20 carbon atoms
- X 1 , X 2 and X 3 are independently -O- or -NR N-
- RN is hydrogen. It is a monovalent organic group having 1 to 20 carbon atoms which may have an atom or a substituent.
- ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising at least one of a photopolymerization initiator and a thermal polymerization initiator.
- ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a photopolymerization initiator.
- ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 11> A laminated body containing two or more layers made of the cured product according to ⁇ 10> and containing a metal layer between any of the layers made of the cured product.
- ⁇ 12> A method for producing a cured product, which comprises a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 9> onto a substrate to form a film.
- the method for producing a cured product according to ⁇ 12> which comprises an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
- the method for producing a cured product according to ⁇ 12> or ⁇ 13> which comprises a heating step of heating the film at 50 to 450 ° C.
- a semiconductor device comprising the cured product according to ⁇ 10> or the laminate according to ⁇ 11>.
- a cured product having excellent chemical resistance can be obtained, a resin composition having excellent storage stability, a cured product obtained by curing the resin composition, a laminate containing the cured product, and the cured product. And a semiconductor device containing the cured product or the laminate.
- the present invention is not limited to the specified embodiments.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
- the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or.
- Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic”, or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the 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 the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified.
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series.
- the molecular weights shall be measured using THF (tetrahydrofuran) as an eluent.
- NMP N-methyl-2-pyrrolidone
- the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
- UV rays ultraviolet rays
- a third layer or element may be further 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 on the base material is referred to as "upper", or if 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 a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C.
- the atmospheric pressure is 101,325 Pa (1 atmospheric pressure)
- the relative humidity is 50% RH.
- a combination of preferred embodiments is a more preferred embodiment.
- the resin composition of the present invention (hereinafter, also simply referred to as “resin composition”) is one or more compounds B selected from the group consisting of polyamic acid esters, phosphate esters, phosphate ester amides and phosphate amides. (Hereinafter, also simply referred to as "Compound B").
- the resin composition of the present invention is preferably a photosensitive resin composition.
- the resin composition may be a negative type resin composition or a positive type resin composition, but a negative type resin composition is preferable.
- the negative type resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when a layer formed from the resin composition is exposed.
- the positive type resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when a layer formed from the resin composition is exposed.
- the resin composition of the present invention preferably further contains at least one of a photopolymerization initiator and a thermal polymerization initiator, and more preferably further contains a photopolymerization initiator. By containing a photopolymerization initiator, it can be used as a negative type resin composition. Further, by containing the thermal polymerization initiator, it can be used as a negative type resin composition or a positive type resin composition.
- the resin composition of the present invention is excellent in chemical resistance of the obtained cured product.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- the resin composition of the present invention contains a polyamic acid ester.
- the polyamic acid ester means that the ratio (%) of the molar amount of the amic acid ester structure to the total molar amount of all the amic acid structures and the amic acid ester structures contained in the resin is 50% or more.
- the ratio (%) of the molar content is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more.
- the upper limit of the ratio (%) of the content of the mole content is not particularly limited and may be 100%.
- the resin composition of the present invention is considered to be excellent in storage stability.
- compound B is considered to strongly interact with the polyamic acid ester. It is presumed that this interaction improves the plasticity of the film before curing (for example, the photosensitive film) and improves the mobility of the partial structure of the resin in the film before curing.
- the pre-cured film made of the resin composition of the present invention is imidized by thermal imidization, chemical imidization, or the like, the motility of the amic acid ester structural portion in the polyamic acid ester is improved, and imidization becomes easier. Since the imidization rate in the finally obtained cured product increases, it is presumed that the chemical resistance is excellent. Since the cured product has excellent chemical resistance, for example, another curable resin composition containing a solvent is further applied and cured on the cured product obtained by curing the curable resin composition of the present invention, and the laminated body is cured.
- a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP)
- an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution
- TMAH tetramethylammonium hydroxide
- a radically polymerizable group is introduced into at least one of the compound B and the polyamic acid ester, a three-dimensional crosslink is efficiently formed and the chemical resistance is further improved.
- the plasticity of the film before curing when the resin composition has photosensitivity, the structural change of the photosensitizer itself in the film before curing and the change in the polymerization of the polymerizable compound caused by the structural change occur. Since it is likely to occur, it is presumed that the resolution will be improved. Further, it is presumed that the cured product obtained from the resin composition of the present invention is also excellent in film strength due to the increase in the imidization rate due to the above interaction.
- Patent Documents 1 and 2 do not describe or suggest a resin composition containing a polyamic acid ester and compound B.
- the resin composition of the present invention contains a polyamic acid ester (hereinafter, also referred to as "specific resin"). Further, the polyamic acid ester preferably contains a repeating unit represented by the formula (2) described later.
- the polyamic acid ester preferably has a polymerizable group.
- the polymerizable group in the polyamic acid ester include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group.
- a radical polymerizable group such as an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group, and a (meth) acryloyloxy group is preferable.
- the polyamic acid ester preferably contains a radically polymerizable group.
- the resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described later as a photosensitizer, and is described later. It is more preferable to contain a radical cross-linking agent, and it is further preferable to contain a photoradical polymerization initiator described later as a photosensitizer, a radical cross-linking agent described later, and a sensitizer described later. From such a resin composition, for example, a negative photosensitive layer is formed.
- the polyamic acid ester may have a polar conversion group such as an acid-degradable group.
- the resin composition contains a photoacid generator described later as a photosensitive agent. From such a resin composition, for example, a chemically amplified positive photosensitive layer or a negative photosensitive layer is formed.
- polyamic acid ester The type of the polyamic acid ester used in the present invention is not particularly specified, but it is preferable that the polyamic acid ester contains a repeating unit represented by the following formula (2).
- a 1 and A 2 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. However, at least one of R 113 and R 114 is a monovalent organic group.
- a 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
- R 111 in the formula (2) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
- a cyclic aliphatic group having 3 to 20, 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 hydrocarbon group of the ring member is a heteroatom. It may be substituted with a group containing.
- Preferred embodiments of the present invention exemplify the groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably the groups represented by -Ar-L-Ar-.
- Ar is an aromatic group independently
- L is a single bond, 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.
- R 111 is preferably derived from diamine.
- the diamine used for producing the polyamic acid ester include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines 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.
- the diamine containing the above is preferable, and the diamine 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 hydrocarbon group of the ring member is a heteroatom. It may be substituted with a containing group.
- groups containing aromatic groups include:
- * represents a binding site with another structure.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 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;
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
- a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
- R 111 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
- Ar is an aromatic group independently
- 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 which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO2- . ..
- 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 formula (61) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and * independently represents a bonding site with a nitrogen atom in the formula (2).
- the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
- R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
- Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
- R 115 in the 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 formula (6) is more preferable.
- * independently represents a binding site with another structure.
- R 112 is a single bond or divalent linking group, which may be replaced with a single bond or a fluorine atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, It is preferably a group selected from -CO-, -S-, -SO 2- , and -NHCO-, and a combination thereof, and is a single bond, which may be substituted with a fluorine atom and has 1 to 1 carbon atoms.
- it is a group selected from 3 alkylene groups, -O-, -CO-, -S- and -SO 2- , and -CH 2- , -C (CF 3 ) 2- , -C ( CH 3 ) It is more preferably a divalent group selected from the group consisting of 2-, -O-, -CO-, -S- and -SO 2- .
- R 111 may have a structure containing a polymerizable group.
- R 111 may have a structure derived from a diamine compound having a polymerizable group.
- the diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and is a compound having a structure in which a structure containing an amino group and a polymerizable group is directly linked to the aromatic ring structure. Is more preferable.
- a group having an ethylenically unsaturated bond, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group and a (meth) acryloxy are preferable.
- a group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
- R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
- the polyamic acid ester may contain only one type of tetracarboxylic dianhydride residue or two or more types as a structure corresponding to R 115 .
- 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 the formula (2), and the preferred range is also the same.
- tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-.
- PMDA pyromellitic acid dianhydride
- 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride 3,3', 4,4'-.
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
- R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
- R 113 and R 114 in the formula (2) independently represent a hydrogen atom or a monovalent organic group, respectively.
- the monovalent organic group preferably contains 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 contains a polymerizable group, and it is more preferable that both contain a polymerizable group.
- at least one of R 113 and R 114 contains two or more polymerizable groups.
- the polymerizable group a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
- 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 preferable.
- Examples of the group 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 the vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group.
- R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
- * 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 alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
- alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group,
- the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded.
- the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
- the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
- the alkylene group may have a substituent.
- Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
- 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.
- the polyalkyleneoxy group from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes.
- a group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
- the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
- the polyamic acid ester when R 113 is a hydrogen atom or R 114 is a hydrogen atom, the polyamic acid ester may form a salt with a tertiary amine compound having an ethylenically unsaturated bond. good.
- the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
- R 113 and R 114 may be a polar conversion group such as an acid-degradable group.
- the acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group.
- a tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
- the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
- examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
- the polyamic acid ester has a fluorine atom in its structure.
- the fluorine atom content in the polyamic acid ester is preferably 10% by mass or more, and more preferably 20% by mass or less.
- the polyamic acid ester may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
- the repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyamic acid esters used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyamic acid ester, it becomes possible to further widen the range of the exposure latitude. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing 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 it is preferable that both are groups containing a polymerizable group.
- a 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. .. R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
- the polyamic acid ester may contain one type of repeating unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyamic acid ester may contain other types of repeating units in addition to the repeating units of the above formula (2).
- the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units.
- the total content is more preferably 70 mol% or more, further 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 the repeating units in the polyamic acid ester except the terminal may be the repeating unit represented by the formula (2).
- the weight average molecular weight (Mw) of the polyamic acid ester is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
- the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
- the degree of dispersion of the molecular weight of the polyamic acid ester is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more.
- the upper limit of the dispersity of the molecular weight of the polyamic acid ester is not particularly defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
- the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
- the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamic acid ester are preferably in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyamic acid esters as one resin are each within the above ranges.
- the polyamic acid ester is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent.
- a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with diamine is more preferable.
- the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-discusin imidazole carbonate and trifluoroacetic anhydride.
- alkylating agent examples include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dialkylformamidedialkylacetal, trimethyl orthoformate, triethyl orthoformate and the like.
- halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
- organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, but is 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 polyamic acid ester, it is preferable to add a basic compound during the reaction.
- the basic compound may be one kind or two or more kinds.
- 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. Examples thereof include pyridine and the like.
- -End sealant- In the method for producing a polyamic acid ester, it is preferable to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyamic acid ester in order to further improve the storage stability.
- examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of properties, it is more preferable to use monoalcohol, phenols and monoamines.
- Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol.
- Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
- Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 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 -Aminobenzene sulfonic acid, 3-amino-4,6-di
- encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
- Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic acid anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like.
- Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride and 1-adamantancarbonyl chloride.
- Heptafluorobutyryl chloride stearate chloride, benzoyl chloride, and the like.
- the production of the polyamic acid ester may include a step of precipitating a solid. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it can be precipitated as a solid, and by drying, a polyamic acid ester or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyamic acid ester may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
- the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention contains at least two kinds of resins.
- the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
- the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyamics that are polyamic acid esters and have different structures derived from dianhydride (R 115 in the above formula (2)). It preferably contains an acid ester.
- the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
- Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
- a (meth) acrylic resin a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
- a high polymerizable base value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group contained in 1 g of the resin. (1 ⁇ 10 -3 mol / g or more)
- a (meth) acrylic resin By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
- the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred. Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
- the content of the other resin may be low.
- 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, based on the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable.
- the lower limit of the content is not particularly limited, and may be 0% by mass or more.
- the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention contains one or more compounds B selected from the group consisting of phosphate esters, phosphate ester amides and phosphate amides.
- the phosphoric acid ester means a compound having at least one phosphoric acid ester structure and not having a phosphoric acid amide structure.
- the phosphate ester amide refers to a compound having at least one phosphate ester structure and at least one phosphate amide structure.
- the phosphoric acid amide means a compound having at least one phosphoric acid amide structure and not having a phosphoric acid ester structure.
- compound B is preferably a compound containing a polymerizable group.
- the polymerizable group contained in the compound B include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, an alkoxysilyl group, a blocked isocyanate group and an oxazolyl group.
- a radically polymerizable group, an epoxy group or an alkoxysilyl group is preferable, and a radically polymerizable group is more preferable.
- the radically polymerizable group a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acrylamide group, a (meth) acryloyloxy group and the like, and a (meth) acryloyloxy group is preferable.
- the alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but a dialkoxysilyl group or a trialkoxysilyl group is preferable, and a trialkoxysilyl group is more preferable.
- the number of carbon atoms of the alkoxy in the alkoxysilyl group is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 2.
- Compound B may contain only one polymerizable group or may contain two or more, but from the viewpoint of chemical resistance of the obtained cured product, it is preferably contained in two or more, and more preferably 2 to 10. It is preferable, and it is more preferable to include 3 to 6.
- compound B contains two or more polymerizable groups, the structures of the respective polymerizable groups may be the same or different.
- the content of the polymerizable group in compound B is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.01 mol / g.
- Compound B preferably contains a compound represented by the following formula (1).
- R 1 , R 2 and R 3 are monovalent organic groups having 1 to 20 carbon atoms which may independently have a hydrogen atom or a substituent, respectively, and are R 1 , R 2 and R 3. At least one of R 3 is a monovalent organic group having 1 to 20 carbon atoms, X 1 , X 2 and X 3 are independently -O- or -NR N- , and RN is hydrogen. It is a monovalent organic group having 1 to 20 carbon atoms which may have an atom or a substituent.
- R 1 , R 2 and R 3 are preferably monovalent organic groups having 1 to 20 carbon atoms which may independently have a substituent.
- R 1 , R 2 and R 3 are preferably a monovalent organic group containing no polymerizable group, or a monovalent organic group containing a polymerizable group, and a monovalent organic group containing a polymerizable group. Is preferable.
- it is preferable that at least one of R 1 , R 2 and R 3 is a monovalent organic group containing a polymerizable group, and at least two are monovalent organic groups containing a polymerizable group. It is preferable that all three are monovalent organic groups containing a polymerizable group.
- R 1 , R 2 and R 3 are a monovalent organic group containing a polymerizable group
- a preferred embodiment of the polymerizable group is described as a preferred embodiment of the polymerizable group contained in the above-mentioned compound B.
- these polymerizable groups may be the same or different.
- the monovalent organic group R 1 , R 2 or R 3 containing a polymerizable group is preferably a group represented by the following formula (P-1).
- L 1 represents a single bond or m + 1 valent linking group
- a 2 represents a polymerizable group
- m represents an integer of 1 or more
- * represents X 1 , X 2 or X 3 Represents the binding site with.
- L 1 is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded, preferably a single bond.
- a bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR N- , or a group in which two or more of these are bonded is more preferable, and it is represented by a hydrocarbon group or a bond between a hydrocarbon group and an ether bond. Groups are even more preferred.
- the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
- a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferable. More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
- a 2 represents the polymerizable group described as the polymerizable group contained in the above-mentioned compound B, and the preferred embodiment is also the same.
- m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, and an integer of 1 to 3. Is particularly preferable, and 1 is most preferable.
- m is 1 and L 1 is a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof is also preferable.
- the hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group or a phenylene group.
- the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
- the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded.
- the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
- an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 1 to 10 carbon atoms is further preferable.
- an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable.
- an alkylene group in the (poly) alkyleneoxy group an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, an ethylene group or a propylene group is more preferable, and an ethylene group is further preferable. ..
- the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. preferable.
- R1 , R2 or R3 a group represented by the following formula is preferable, but the group is not limited thereto.
- * represents the binding site with X 1 , X 2 or X 3 in the formula (1)
- R independently represents a hydrogen atom or a methyl group
- Et represents an ethyl group
- n represents an ethyl group. It represents the number of repetitions and is preferably 2 to 10.
- R 1 , R 2 or R 3 which are monovalent organic groups containing no polymerizable group, are independently hydrocarbon groups having 1 to 20 carbon atoms, or hydrocarbon groups, ether bonds, carbonyl groups and thioethers.
- a bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded is preferable, and an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms is preferable.
- the alkoxyalkyl group of is more preferred.
- At least one of X 1 , X 2 and X 3 is preferably —O—, and at least two are more preferably —O—. It is more preferable that all three are —O—.
- at least one of X 1 , X 2 and X 3 is preferably -NR N- , and at least two are more preferably -NR N- . It is more preferable that all three are -NR N- .
- RN preferably represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and further preferably representing a hydrogen atom. .. Further, when there are a plurality of RNs in the equation, these RNs may be the same or different.
- the molecular weight of compound B (in the case of having a molecular weight distribution, the weight average molecular weight) is preferably 150 to 2000, and more preferably 200 to 1000.
- the compound B examples include 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, acid phosphoxyethyl methacrylate, tris phosphate (2-butoxyethyl), triethyl phosphate, triphenyl phosphate, and the like.
- Et represents an ethyl group
- n represents an independent number of repetitions
- an integer of 2 to 10 is preferable.
- the resin composition of the present invention preferably contains 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and 0.5 to 5% of compound B with respect to 100 parts by mass of the resin. It is more preferable to contain% by mass.
- the resin composition of the present invention may contain one type of compound B alone, or may contain two or more types of compound B. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention preferably contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
- esters include 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, and ⁇ -butyrolactone.
- alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
- alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, 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, and ethylene glycol monoethyl ether.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
- cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- Alcohols include 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, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
- the resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat.
- the resin composition of the present invention preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator, and particularly preferably contains a photopolymerization initiator.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
- the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). Is preferable.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a known compound can be arbitrarily used.
- halogenated hydrocarbon derivatives for example, 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 and the like.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification. Further, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No.
- ketone compound for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification.
- Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the contents thereof are described in the present specification. Be incorporated.
- Examples of the ⁇ -hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, and DAROCUR 1173.
- Omnirad 184 Omnirad 1173
- Omnirad 2959 Omnirad 127
- IRGACURE 184 IRGACURE is a registered trademark
- DAROCUR 1173 DAROCUR 1173
- DAROCUR 1173 DAROCUR 1173.
- -2959, IRGACURE 127 (trade name: both manufactured by BASF) can be used.
- Omnirad 907 As the ⁇ -aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 369, all of which are IRGACURE 37. (Manufactured by the company) can be used.
- the aminoacetophenone-based initiator the compound described in JP-A-2009-191179, in which the maximum absorption wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used, and the contents thereof are incorporated in the present specification.
- acylphosphine oxide-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Omnirad 819, Omnirad TPO (all manufactured by IGM Resins BV), IRGACURE-819 and IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
- metallocene compound examples include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.
- the photoradical polymerization initiator is more preferably an oxime compound.
- the oxime compound By using the oxime compound, it becomes possible to improve the exposure latitude more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- oxime compound examples include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
- an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304, TR-PBG-305 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
- Adeka Arkuru's NCI-730, NCI-831 and Adeka Arkuru's NCI-930 are also used. be able to.
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- SpeedCure PDO manufactured by SARTOMER ARCEMA
- an oxime compound having the following structure can also be used.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081, and the contents thereof are incorporated in the present specification.
- 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 the compounds described in WO 2013/083505, the contents of which are incorporated herein.
- an oxime compound having a fluorine atom It is also possible to use an oxime compound having a fluorine atom.
- an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013.
- the compound (C-3) and the like described in paragraph 0101 of the publication No. 164471 are mentioned, and the contents thereof are incorporated in the present specification.
- 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 paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples of the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 are incorporated herein by reference. Further, examples of the oxime compound having a nitro group include ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in the present specification.
- an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
- the electron-attracting group of 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.
- the benzoyl group may have a substituent.
- the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
- 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, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
- the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
- RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
- RX3 to RX14 independently represent a hydrogen atom or a substituent. However, at least one of RX10 to RX14 is an electron-withdrawing group.
- RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 and RX14 are hydrogen atoms.
- oxime compound OX examples include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.
- the most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061. Incorporated herein.
- the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
- a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound.
- Compounds are preferred.
- photoradical polymerization 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 a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is further preferable. ..
- the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
- -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkyl benzoin
- benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R I00 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, and the like.
- RI01 is a group represented by the formula (II). It is the same group as RI00 , and RI02 to RI04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the photoradical polymerization initiator the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents thereof are incorporated in the present specification.
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
- two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved. ..
- bifunctional or trifunctional or higher functional photo-radical polymerization initiator are described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675.
- G) the oxime esters photoinitiator described in paragraph No. 0007 of Cmpd1-7 described in International Publication No. 2016/034943, JP-A-2017-523465, JP-A-2017-167399.
- the content thereof 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 of the present invention. It is more preferably 0.5 to 15% by mass, and even 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 kinds of photopolymerization initiators are contained, the total amount is preferably in the above range. Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
- the resin composition may contain a sensitizer.
- the sensitizer absorbs specific active radiation and becomes an electronically excited state.
- the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
- Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo.
- Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
- sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
- 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. It is more preferably present, and even more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the resin composition of the present invention may contain a chain transfer agent.
- Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
- Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule.
- Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- thiol compounds can be preferably used.
- 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 of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is further preferable.
- the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a photoacid generator.
- the photoacid generator represents a compound that generates at least one of Bronsted acid and Lewis acid by irradiation with light of 200 nm to 900 nm.
- the irradiated light is preferably light having a wavelength of 300 nm to 450 nm, and more preferably light having a wavelength of 330 nm to 420 nm.
- the photoacid generator is a photoacid generator capable of generating an acid by being exposed to light when used alone or in combination with a sensitizer.
- generated acids include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivative, phosphorus derivative, antimony derivative, halogen peroxide, etc. Sulfonamide and the like are preferably mentioned.
- Examples of the photoacid generator used in the resin composition of 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 preferable from the viewpoint of sensitivity and storage stability, and oxime esters are preferable from the viewpoint of mechanical properties of the film to be formed.
- the quinone diazide compound is a monovalent or polyvalent hydroxy compound with an ester bond of quinone diazide sulfonic acid, a monovalent or polyvalent amino compound with quinone diazide sulfonic acid conjugated with a sulfonamide, and a polyhydroxypolyamino compound with quinone diazide.
- Examples thereof include those in which the sulfonic acid of the above is ester-bonded and / or sulfonic acid-bonded.
- All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that 40 mol% or more of all the functional groups are substituted with quinonediazide on average. ..
- a quinone diazide compound By containing such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray. ..
- hydroxy compound phenol, trihydroxybenzophenone, 4methoxyphenol, 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, Methylenetris-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, Tri
- the 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 can be mentioned, but the present invention is not limited thereto.
- polyhydroxypolyamino compound examples include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. ..
- the quinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl 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 of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin. It is preferable to set the content of the quinonediazide compound in this range because the contrast between the exposed portion and the unexposed portion can be obtained and the sensitivity can be further increased. Further, a sensitizer or the like may be added as needed.
- the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
- the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
- X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s exist, they may be the same or different from each other.
- the alkyl group and the alkoxy group in X3 may have a substituent.
- As the alkyl group in X3 a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.
- As the alkoxy group in X3 a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.
- halogen atom in X3 a chlorine atom or a fluorine atom is preferable.
- m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3 , the plurality of X3s may be the same or different.
- R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxy group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be 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, an alkyl halide group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms.
- m3 is 3
- X3 is a methyl group
- the substitution position of X3 is the ortho position
- R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,
- a compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
- oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
- R s1 represents an alkyl group, an aryl group or a heteroaryl group
- R s2, which may be present in a plurality of R s2 independently represents a hydrogen atom, an alkyl group and an aryl group
- R s6 which represents a group or a halogen atom and may be present in a 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 from 0 to 6.
- an alkyl group represented by R s1 preferably 1 to 30 carbon atoms
- an aryl group preferably 6 to 30 carbon atoms
- a heteroaryl group carbon
- 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 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms).
- Hydrogen atom or alkyl group is more preferable.
- the Rs2 that may be present in two or more in the compound, 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. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
- 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, and is preferably O.
- the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
- ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
- the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
- the alkyloxy group preferably having 1 to 30 carbon atoms
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
- 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-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
- 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 and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
- R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
- R t2 represents a hydrogen atom or a methyl group.
- R t7 represents a hydrogen atom or a bromine atom, and is 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, and a phenyl group.
- it 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. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
- Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674.
- the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
- oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- Ru9 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, and the like. Represents an aryl group or a heteroaryl group.
- R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
- Ru2a 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.
- R u5 to R u7 independently represent an alkyl group or an aryl group, respectively.
- Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group.
- Two of R u1 to R u4 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a fused ring together with the benzene ring.
- R u1 to Ru4 a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of Ru1 to Ru4 are bonded to each other to form an aryl group is also preferable. Above all, it is preferable that all of Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
- the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
- the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
- Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
- the following b-9, b-16, b-31, and b-33 are preferable.
- 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 Kagaku Co., Ltd.), and the like. Can be done.
- organic halogenated compound examples include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, , Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
- an oxazole compound substituted with a trihalomethyl group an S-triazine compound is given as a preferable example. More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-.
- Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710.
- Japanese Patent Application Laid-Open No. 2000-131837 Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent Application Laid-Open No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, etc., and Kunz, Martin "Rad Tech '98.
- organic boron sulfonium complex or the organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561.
- Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like. Incorporated herein.
- disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
- onium salt compound examples include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, European Patents 104, 143, US Patents 339, 049, 410, 201, Japanese Patent Application Laid-Open No. Iodonium salt described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No.
- onium salts examples 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, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 2 carbon atoms.
- Z 11 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable.
- perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinate ion are preferable.
- Ar 21 and Ar 22 each represent an aryl group having 1 to 20 carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
- Z21 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, and a sulfate ion, and is stable and reacts. From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- R 31 , R 32 , and R 33 each have an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may independently have 1 to 6 substituents. It is preferably an aryl group from the viewpoint of reactivity and stability.
- 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, and an alkoxy group having 1 to 12 carbon atoms.
- Examples thereof include an alkylamide group having 1 to 12 or an arylamide group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms.
- Z 31 - represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinate ion, a thiosulfonic acid ion, a sulfate ion, and stability.
- perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- preferable photoacid generators include the following.
- 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 more preferably 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.
- the photoacid generator may be used alone or in combination of two or more. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range. It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.
- the composition of the present invention may contain a thermoacid generator.
- the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
- the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
- the thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
- the acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
- aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
- alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
- haloalkyl sulfonic acid such as sulfonic acid is preferable.
- thermoacid generator include those described in paragraph 0055 of JP2013-072935.
- those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film.
- JP2013-167742A is also preferable as the thermal acid generator.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- the resin composition of the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by a physical or chemical action.
- Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
- the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator.
- the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
- the base generator may be an ionic base generator or a nonionic base generator.
- Examples of the base generated from the base generator include secondary amines and tertiary amines.
- the base generator according to the present invention is not particularly limited, and a known base generator can be used.
- Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides.
- Compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, ⁇ -lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
- Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
- Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, 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, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
- Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
- the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.
- a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
- 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, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms).
- 2-18 is more preferred, 3-12 is more preferred
- ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- Rb 1 and Rb 2 may be coupled to each other to form a ring.
- Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- substituents preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12
- It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- cyclohexyl groups are more preferred.
- Rb 3 examples include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18). ⁇ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable).
- 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24).
- 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbons).
- 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
- Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
- the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
- Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
- Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited.
- Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- 2 to 8 are more preferable, 2 to 3 are more preferable
- aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
- 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
- Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms are preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
- the compound represented by the formula (B1-1) is also preferable.
- Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
- Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further 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 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
- L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more.
- RN1 and RN2 each independently represent a monovalent organic group.
- linking chain refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms).
- L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length”) is 4.
- the number of carbon atoms in L in the formula (B3) is preferably 3 to 24.
- the upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
- the lower limit is more preferably 4 or more.
- the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable.
- the chain length of L is preferably 4 or 5, and most preferably 4.
- Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
- the base generator contains a compound represented by the following formula (N1).
- RN1 and RN2 each independently represent a monovalent organic group
- RC1 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, and 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 is the shortest route between the two carbonyl groups in the equation.
- RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred.
- an aliphatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent.
- an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
- a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain.
- Examples thereof include 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 even more preferably 3 to 12 carbon atoms.
- the linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group.
- Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
- the group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
- Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
- the alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
- the alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later.
- a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
- RN1 and RN2 may be connected to each other to form an annular structure.
- oxygen atoms or the like may be contained in the chain.
- the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
- a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like.
- Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.
- RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
- the protecting group a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
- the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain.
- the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like.
- Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned.
- Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
- the divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable.
- the hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom 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. More preferably, a divalent aromatic hydrocarbon group, or a group relating 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 preferable. It is preferable that these groups do not have an oxygen atom.
- 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 even 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.
- the group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
- 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 chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
- the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- the group related to the combination of the chain alkylene group and the 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.
- the alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
- the alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
- the linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
- the cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- 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 propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
- Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
- the molecular weight of the non-ionic 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 preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
- ammonium salt examples include, but are not limited to, the following compounds.
- iminium salt examples include, but are not limited to, the following compounds.
- 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 of the present invention.
- the lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more.
- the upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
- the base generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound include radical cross-linking agents and other cross-linking agents.
- the resin composition of the present invention preferably contains a radical cross-linking agent.
- the radical cross-linking agent is a compound having a radically polymerizable group.
- a group containing an ethylenically unsaturated bond is preferable.
- Examples of the group containing an ethylenically unsaturated bond include a group having 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.
- a (meth) acryloyl group As the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
- the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds.
- the radical cross-linking agent may have three or more ethylenically unsaturated bonds.
- As the compound having two or more ethylenically unsaturated bonds a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable.
- the compound having is more preferable.
- the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable 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 (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polymorphic acid group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
- Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof.
- the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
- a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
- Compounds having two or more groups and cardo resins can also be used.
- the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable.
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
- TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
- urethane oligomer UAS-10 are examples of the radical cross-linking agent.
- UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
- radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
- 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.
- the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- the radical cross-linking agent provided with the above is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
- the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good.
- the acid value is measured according to the description of JIS K 0070: 1992.
- the resin composition it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
- 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 dimethacrylate.
- the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula 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 control of the elastic modulus of the pattern (cured product).
- Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) 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, allylglycidyl ether and the like 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.
- the bifunctional or higher functional cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
- the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
- the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator.
- a compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof.
- a compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
- a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group.
- a compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
- an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group.
- examples thereof include compounds having a structure substituted with an alkoxymethyl group.
- the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
- the cross-linking agent using melamine is a melamine-based cross-linking agent
- the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
- the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
- a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
- the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine.
- the alkoxymethyl group or acyloxymethyl group contained in 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 contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
- the molecular weight of the compound is preferably 1500 or less, preferably 180 to 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 be bonded to each other to form a ring.
- Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
- X represents a single-bonded or divalent organic group
- each R 104 independently represents an alkyl group or an acyl group
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 4 represents a group that decomposes by the action of an acid to produce an alkali-soluble group
- It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R5 represents a group desorbed by the action
- R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and 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 a group that decomposes by the action of an acid to produce an alkali-soluble group a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ).
- R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be coupled to each other to form a ring.
- 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 alkyl group may be linear or branched.
- 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 fused ring.
- the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
- 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 above-mentioned 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 those of the above-mentioned preferred embodiments of alkyl and aryl groups.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect 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 decomposes by the action of an acid to produce an alkali-soluble group, or the group that is desorbed 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 preferably, it is a tertiary alkyl ester group or an acetal group.
- Examples of the compound having an alkoxymethyl group include the following structures.
- Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
- Examples of the compound 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 compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
- melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
- urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol.
- Uril trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monoethoxymethylated glycol uryl, diethoxymethylated glycol uryl, triethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl , Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol
- Glycoluril-based cross-linking agents such as uryl; Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea,
- benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra Examples thereof include propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which the group of the species is directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
- suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
- 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 lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of 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 to 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. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone.
- n is an integer of 1 to 5
- m is an integer of 1 to 20.
- n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
- oxetane compound compound having an oxetanyl group
- the oxetane compound 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, and the like.
- examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like.
- Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
- benzoxazine compound examples include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo.
- examples include 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, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a ⁇ -ketoester. Examples thereof include compounds and amino compounds.
- silane coupling agent examples include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992.
- examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference.
- silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
- Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
- the content of the metal adhesive improving agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.
- the resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
- the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- 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-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
- Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol
- polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
- the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance with time from exposure to heating.
- the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa.
- the acid trapping agent a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable.
- the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned.
- the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
- Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
- As an acid scavenger having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like.
- Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like.
- aniline derivative having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline and the like.
- preferred acid trapping agents 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-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin
- the composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
- the acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
- the resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained.
- Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries eg, antifoaming agents, flame retardant agents, etc.
- properties such as film physical characteristics can be adjusted.
- 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 a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used.
- the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
- the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, 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 applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
- fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
- F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
- Florard FC430, FC431, FC171, Novek FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
- the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein.
- a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
- the fluorine-based surfactant 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) (meth).
- 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 the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
- hydrocarbon-based surfactant examples include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
- organosiloxane polymer KP-341 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.
- anion-type surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
- the content of the surfactant 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.
- the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
- 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 of the present invention.
- the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
- the resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
- the thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
- the content thereof 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 of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
- the resin composition of the present invention may contain inorganic particles.
- specific examples of the 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 size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
- the average particle size of the inorganic particles is a primary particle size and a 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, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
- salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
- benzophenone-based ultraviolet 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- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
- benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3).
- Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
- the triazine-based ultraviolet absorber 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-triazin
- the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
- the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
- Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
- Specific examples of the organic titanium compound are shown in I) to VII) below:
- I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained.
- Specific examples include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate), and titanium diisopropoxiside bis (2,4-pentanegeonate).
- Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
- Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
- Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
- Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
- the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
- -Pyrrole-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 with respect to 100 parts by mass of the specific resin.
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
- the composition of the present invention may contain an antioxidant.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
- the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
- the phenol compound any phenol compound known as a phenolic antioxidant can be used.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
- a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
- a phosphorus-based antioxidant can also be preferably used.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
- the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
- the composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- 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 an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group.
- R 7 represents a 1- 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 the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
- metal oxidation can be suppressed by the rust preventive action on the metal material.
- R 7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group and a heterocyclic group.
- -O-, -NH-, -NHNH-, a combination thereof and the like can be mentioned, and may further have a substituent.
- alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion
- -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
- Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
- the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin.
- the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, photosensitive is exhibited.
- 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 may be used. When two or more types 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, if necessary.
- the antiaggregating agent include sodium polyacrylate and the like.
- one type of anti-aggregation agent 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 an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
- the resin composition of the present embodiment may contain a phenolic compound, if necessary.
- phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP.
- 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 when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
- Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof.
- the other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
- one type of other polymer 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 other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content 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 of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 3,000 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film.
- the coated surface condition may deteriorate. ..
- the water content of the resin composition of 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 2.0% or more, the storage stability of the resin composition may be impaired. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
- the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm.
- the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
- the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention.
- examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
- the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
- a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing contamination of raw materials and the resin composition of the present invention with impurities. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
- the curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C.
- the form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape.
- the cured product is preferably in the form of a film.
- this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape.
- the film thickness of this cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
- the shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
- the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
- the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
- the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
- the resin composition of the present invention can be prepared by mixing each of the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used. For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
- the temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
- the filter hole diameter may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene).
- the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use.
- filters having different pore diameters or materials may be used in combination.
- the connection mode include a mode in which an HDPE filter having a hole diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 ⁇ m is connected in series as the second stage.
- various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration.
- the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
- the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. Further, in the method for producing a cured product of the present invention, the film forming step, the exposure step of selectively exposing the film formed by the film forming step, and the film exposed by the exposure step are developed using a developing solution. It is more preferable to include a developing step of forming a pattern.
- the method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step for heating the pattern obtained by the developing step and the post-development for exposing the pattern obtained by the developing step.
- the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
- the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
- the resin composition of the present invention can be applied to a substrate to form a film and can be used in a film forming step.
- the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
- the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, and Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition, etc.). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited.
- semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film
- a metal base material such as a magnetic film, a reflective film, Ni, Cu,
- a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable. Further, 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 thereof.
- the shape of the base material is not particularly limited, and may be circular or rectangular. The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
- a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used as the base material.
- a resin composition when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
- Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
- the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
- An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity.
- the method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
- the coating method can be appropriately selected depending on the shape of the substrate.
- a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
- the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
- a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
- EBR edge bead rinse
- a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
- the film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
- the drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
- the film may be subjected to an exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step. Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
- the exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
- the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
- the exposure wavelengths are as follows: (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-ray (wavelength).
- the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
- the exposure light used for exposure includes light having a wavelength of 405 nm.
- the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
- the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
- the post-exposure heating step can be performed after the exposure step and before the developing step.
- the heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
- the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
- the heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature. Further, the heating rate may be appropriately changed during heating.
- the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
- the film after exposure may be subjected to a developing step of developing with a developing solution to form a pattern.
- the method for producing a cured product of the present invention may include a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern.
- a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern By performing the development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
- the development in which the non-exposed portion of the film is removed by the developing step is called negative type development
- the development in which the exposed portion of the film is removed by the developing step is called positive type development.
- Examples of the developing solution used in the developing step include an alkaline aqueous solution or a developing solution containing an organic solvent.
- the developing solution is an alkaline aqueous solution
- examples of the basic compound that the alkaline aqueous solution can 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, Tetrapentyl Ammonium Hydroxide, Tetrahexyl Ammonium Hydroxide, Tetraoctyl Ammonium Hydroxide, Ethyltrimethylammonium Hydroxide , Butyltrimethylammonium Hydroxide, Methyltriamylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, dimethylbis (2-Hydroxyethyl) Ammonium Hydroxide, tri
- the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.
- the organic solvent may be used as esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, etc.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxy
- ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, Ethyl 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, propylene Glycolmonopropyl ether acetate and the like, and as ketones
- Aromatic hydrocarbons such as toluene, xylene and anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol and diethylene glycol as alcohols.
- Preferable examples thereof include propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like
- examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.
- the developer contains an organic solvent
- one type or a mixture of two or more types of organic solvent can be used.
- a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and ⁇ -butyrolactone are preferable.
- a developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
- the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable. Further, the content may be 100% by mass.
- the developer may further contain other components.
- other components include known surfactants and known defoaming agents.
- the method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
- the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
- the method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate.
- a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
- the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the developing solution is an alkaline aqueous solution
- water can be used as the rinsing solution.
- the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
- the esters include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Eth
- Ethyl acid acid, etc. methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc.
- ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran.
- Ethyl Glycol Monomethyl Ether Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example.
- ketones for example, methyl ethyl ketone, cyclohexanone, cycl
- Aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols.
- Propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
- the rinsing liquid contains an organic solvent
- one type or a mixture of two or more types of organic solvent can be used.
- cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.
- the rinsing liquid contains an organic solvent
- 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
- the rinse liquid may be 100% by mass of an organic solvent.
- the rinse solution may further contain other components.
- other components include known surfactants and known defoaming agents.
- the method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid to the base material by filling, and the method of supplying the rinsing liquid to the base material by a shower.
- the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying with a spray nozzle is more preferable.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
- the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
- a method of supplying the rinse liquid in the rinsing step a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
- a process of vibrating with a sonic or the like and a process of combining them can be adopted.
- the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step. In the heating step, the resin such as polyamic acid ester is cyclized to become a resin such as polyimide.
- the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
- the heating step is preferably a step of promoting the cyclization reaction of the polyamic acid ester in the pattern by the action of the base or the like generated from the base generator by heating.
- the heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature.
- the temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min.
- the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
- 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 to the maximum heating temperature is started.
- the resin composition of the present invention when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention.
- the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
- the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
- 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 performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step.
- the pretreatment step may be performed in 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.
- the heating step is preferably carried out in an atmosphere having a low oxygen concentration 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, and more preferably 20 ppm (volume ratio) or less.
- the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
- the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step.
- the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
- the post-development exposure step for example, a reaction in which cyclization of a polyamic acid ester proceeds due to exposure to a photobase generator, a reaction in which acid-decomposable groups are removed due to exposure to a photoacid generator, etc. are promoted. can do.
- the post-development exposure step at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
- the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
- the post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
- the pattern obtained by the developing step may be subjected to the metal layer forming step of forming the metal layer on the pattern.
- the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one provided in at least one of a heating step and a post-development exposure step). Is preferable.
- metal layer existing metal species can be used without particular limitation, and examples thereof 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 for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do.
- photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination of these can be considered.
- a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
- Preferred embodiments of plating include electrolytic plating 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 in the thickest portion.
- Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd.
- the method for producing a cured product of the present invention, or the cured product of the present invention is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
- the laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
- the laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
- the two or more layers made of the cured product contained in the laminated body at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
- the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.
- the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product.
- the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times.
- the preferred embodiment of the metal layer forming step is as described above.
- a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
- the resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
- the method for producing a laminated body of the present invention preferably includes a laminating step.
- the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step and development are performed again on the surface of a pattern (resin layer) or a metal layer. It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of the film forming step (a), the heating step, and the post-development exposure step may be repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
- the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step.
- Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
- the laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
- a structure having two or more and 20 or less resin layers such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
- the composition, shape, film thickness, etc. of each of the above layers may be the same or different.
- a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided.
- a film forming step an exposure step, (c) a developing step, (d) at least one of a heating step and a post-development exposure step (e) a metal layer forming step is repeated in this order.
- a film forming step an exposure step
- a developing step a developing step
- a metal layer forming step is repeated in this order.
- a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step is repeated in this order.
- the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
- the surface activation treatment step is usually performed after the metal layer forming step, but after the development step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
- the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each.
- the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer.
- the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
- the resin composition layer when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
- Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 .
- the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
- the present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.
- the present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention.
- the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
- the weight average molecular weight of the obtained A-1 (gel permeation chromatography (eluent: polystyrene-equivalent value of NMP (N-methyl-2-pyrrolidone)) was 31000.
- the measurement conditions are as follows. Column: TSKguardcumn SuperAW-H (4.6 mm ID. ⁇ 35 mm) 1 bottle TSK SuperAWM-H (6.0 mm ID.
- the mixture was then heated to room temperature and stirred for 2 hours, then 2 mL of ethanol was added and the mixture was stirred for 1 hour, and 50 mL of ⁇ -butyrolactone was added.
- the precipitate formed in the reaction mixture was then removed by filtration to form a precipitate in 500 mL of ethanol, the resulting precipitate was filtered off and then dissolved in 250 mL of tetrahydrofuran.
- the obtained solution was added dropwise to 4 liters of water to precipitate the polyimide precursor resin, the water-polyimide precursor resin mixture was stirred at a rate of 5000 rpm for 15 minutes, and the polyimide precursor was filtered. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyamic acid ester A-5. Mw was 30,000.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. -1 was obtained in an amount of 45.3 g (yield 87%). It was confirmed by 1 H-NMR that the structure of the obtained B-1 was a structure represented by the following chemical formula.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. -2 was obtained in 35.7 g (yield 85%). It was confirmed by 1 H-NMR that the structure of the obtained B-2 was a structure represented by the following chemical formula.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. 3 was obtained in an amount of 26.5 g (yield 83%). It was confirmed by 1 H-NMR that the structure of the obtained B-3 was a structure represented by the following chemical formula.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. 42.3 g (yield 90%) of -4 was obtained. It was confirmed by 1 H-NMR that the structure of the obtained B-4 was represented by the following chemical formula.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. 52.0 g (yield 91%, isomer mixture) of -6 was obtained. It was confirmed by 1 H-NMR that the structure of the obtained B-6 was a structure represented by the following chemical formula.
- the insoluble material was filtered off, 1000 mL of ethyl acetate was added to the filtrate, the organic phase was washed with 1N (1 mol / L) hydrochloric acid, and then washed with water three times. After adding magnesium sulfate to the organic phase and drying, the insoluble material is filtered off, 4-hydroxy-TEMPO (0.05 g) is added to the filtrate, and the solvent is distilled off under reduced pressure to distill off the phosphoric acid compound B. -7 was obtained in an amount of 42.3 g (yield 90%). It was confirmed by 1 H-NMR that the structure of the obtained B-7 was a structure represented by the following chemical formula.
- Examples and comparative examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Further, in each comparative example, the components shown in the following table were mixed to obtain each comparative composition. Specifically, the content of the components other than the solvent described in the table is the amount (parts by mass) described in each "addition amount" column of the table. Regarding A-6, the amount of solid content in the solution was added so as to be the amount (part by mass) described in each "addition amount” in the table. The obtained resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m.
- the description of "-" indicates that the composition does not contain the corresponding component.
- A-2 / A-3 50/50
- A-2 and A-3 are A-2: 50 parts by mass and A-3: 50 parts by mass. It is shown that it was contained in.
- the description of "addition amount” of "solvent” indicates the total content (parts by mass) of the mixed solvent having the above content ratio.
- B-1 to B-7 B-1 to B-7 synthesized in the above synthesis example.
- ⁇ B-8 MR-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
- B-9 MR-260 (manufactured by Daihachi Chemical Industry Co., Ltd.)
- B-10 Hosmer M (manufactured by Unichemical)
- B-11 Tris phosphate (2-butoxyethyl) B-1 to B-11 are all compounds corresponding to the above-mentioned compound B.
- each prepared resin composition or comparative composition was applied onto a silicon wafer by a spin coating method to form a thermosetting resin composition layer.
- the silicon wafer to which the obtained thermosetting resin composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform thermosetting resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer. rice field. This value (15 ⁇ m) was taken as the pre-time film thickness. [Film thickness after aging]
- each of the prepared resin compositions or comparative compositions was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C.
- thermosetting resin composition layer was formed by applying it on a silicon wafer by a spin coating method using the same number of revolutions as obtained.
- the silicon wafer to which the obtained thermosetting resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform thermosetting resin composition layer on the silicon wafer.
- the film thickness of the obtained thermosetting resin composition layer was measured, and this value was taken as the film thickness after aging.
- the film thickness of the resin composition layer on the substrate was measured using an optical interferometry film thickness measuring device (Lambda Ace VM-1030 manufactured by Dainippon Screen Mfg. Co., Ltd.).
- the refractive index was measured as 1.629 for polyimide.
- a film thickness change rate of less than 10% was judged to be OK, and a film thickness change rate of 10% or more was judged to be NG.
- the evaluation results are described in the "storage stability" column in the table.
- each thermosetting resin composition or comparative composition prepared was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
- the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform thermosetting resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer. ..
- the resin composition layer was fully exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C). In the example in which the photopolymerization initiator was not contained in the composition, no exposure was performed.
- thermosetting resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10 ° C./min using a box oven to reach the “curing temperature (° C.)” in the table. After reaching the stated temperature, the temperature was maintained for 3 hours.
- the cured resin layer (cured product) was immersed in a 4.9 mass% hydrofluoric acid solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched out using a punching machine to prepare a test piece having a width of 3 mm and a sample length of 30 mm.
- the obtained test piece was subjected to JIS-K6251: using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity) in the longitudinal direction of the film. Measured according to 2017. The evaluation was carried out 5 times each, and the arithmetic mean value of the above 5 measurement results was used as an index value for the elongation rate (breaking elongation rate) when the film was broken. The evaluation was performed according to the following criteria, and the evaluation results are described in the "Membrane strength" column in the table. It can be said that the larger the elongation at break (the above index value), the higher the film strength.
- the prepared resin composition or comparative composition was applied onto a silicon wafer by a spin coating method, respectively, to form a curable resin composition layer.
- the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
- the resin composition layer was fully exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C). In the example in which the photopolymerization initiator was not contained in the composition, no exposure was performed.
- the obtained resin composition layer (resin layer) is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in "curing temperature (° C.)" in the table, and then.
- a cured product was formed on the silicon wafer.
- the cured product was not peeled from the silicon wafer, and the cured product and the silicon wafer were immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
- Chemical solution Mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the resin layer in the chemical solution at 75 ° C.
- DMSO dimethylsulfoxide
- TMAH tetramethylammonium hydroxide
- the dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above.
- the evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column in the table. It can be said that the smaller the dissolution rate, the better the chemical resistance.
- -Evaluation criteria A The dissolution rate was less than 200 nm / min.
- B The dissolution rate was 200 nm / min or more and less than 300 nm / min.
- C The dissolution rate was 300 nm / min or more and less than 400 nm / min.
- D The dissolution rate was 400 nm / min or more and less than 500 nm / min.
- E The dissolution rate was 500 nm / min or more.
- the prepared resin composition or comparative composition was applied onto a silicon wafer by a spin coating method, respectively, to form a resin composition layer.
- the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
- the resin composition layer on the silicon wafer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
- the exposure was performed via a mask (a binary mask in which the pattern was 1: 1 line and space and the line width was 5 to 20 ⁇ m and the line width was formed in 1 ⁇ m increments).
- a mask a binary mask in which the pattern was 1: 1 line and space and the line width was 5 to 20 ⁇ m and the line width was formed in 1 ⁇ m increments.
- cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a line-and-space pattern of the resin composition layer.
- PMEA propylene glycol monomethyl ether acetate
- the obtained resin composition layer was heated in a nitrogen atmosphere at a heating rate of 10 ° C./min using a box oven to reach the temperature described in "Curing temperature (° C.)" in the table.
- Example 51 In Example 1, except that the heating means for heating at the "curing temperature (° C.)" in the table was changed from the box oven to the "infrared lamp heating device (manufactured by Advance Riko Co., Ltd., RTP-6)".
- the above-mentioned film strength, chemical resistance and resolution were evaluated by the same method as in Example 1.
- the specific heating conditions are such that the temperature is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and the temperature is maintained for 3 hours after reaching the temperature described in "Curing temperature (° C.)" in the table. The condition was to do.
- the evaluation results of film strength, chemical resistance and resolution in Example 51 were the same as those evaluation results in Example 1, respectively.
- Example 52 the resolution was evaluated by the same method as in Example 22 except that the exposure light source was changed from the stepper (Nikon NSR 2005 i9C) to the direct exposure device (Adtech DE-6UH III). The exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a 1: 1 line-and-space pattern with a line width of 5 to 20 ⁇ m in 1 ⁇ m increments. The exposure amount was 500 mJ / cm 2 . The evaluation result of the resolution in Example 52 was the same as the evaluation result of the resolution in Example 22.
- Example 53 In Example 22, the above-mentioned film strength, chemical resistance and resolution were evaluated by the same method as in Example 22 except that the exposure with i-line was changed to the exposure with light having a wavelength of 405 nm. .. The evaluation results of film strength, chemical resistance and resolution in Example 53 were the same as those evaluation results in Example 22, respectively.
- the resin composition according to the present invention has excellent storage stability, and the cured product obtained from the resin composition according to the present invention has excellent chemical resistance.
- the comparative compositions according to Comparative Examples 1 and 2 do not contain compound B. It can be seen that the cured product obtained from such a comparative composition is inferior in chemical resistance.
- a polyamic acid is used as the resin instead of the polyamic acid ester. It can be seen that such a comparative composition is inferior in storage stability.
- Example 101 The resin composition used in Example 1 was applied in layers on the surface of a resin substrate having a thin copper layer formed on the surface by a spin coating method, dried at 100 ° C. for 4 minutes, and had a resin composition having a film thickness of 20 ⁇ m. After forming the material layer, the material was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
- a mask a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
- the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer.
- the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.
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Abstract
Description
このような樹脂組成物を、例えば塗布等により基材に適用して樹脂膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化物を基材上に形成することができる。
上記ポリアミック酸エステルは、例えば加熱により環化され、硬化物中でポリイミドとなる。
樹脂組成物は、公知の塗布方法等により適用可能であるため、例えば、適用される樹脂組成物の適用時の形状、大きさ、適用位置等の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミドが有する高い性能に加え、このような製造上の適応性に優れる観点から、上述の樹脂組成物の産業上の応用展開がますます期待されている。
特許文献2には、(A)特定構造のリン化合物、(B)有機溶媒に可溶なポリアミド酸及び/又は有機溶媒に可溶なポリイミド、(C)C、H、O、N原子のみからなる、分子中に少なくとも1個以上の炭素-炭素二重結合を有する化合物、(D)光反応開始剤を必須成分とする感光性樹脂組成物であって、上記(C)成分は少なくとも2種類の異なる化合物を用いるとともに、1種以上の(メタ)アクリレート化合物を含むことを特徴とする感光性樹脂組成物が記載されている。
<1> ポリアミック酸エステルと、
リン酸エステル、リン酸エステルアミド及びリン酸アミドよりなる群から選ばれる1種以上の化合物Bとを含む
樹脂組成物。
<2> 上記ポリアミック酸エステルが、下記式(2)で表される繰り返し単位を含む、<1>に記載の樹脂組成物。
<3> 式(2)における上記R113及びR114の少なくとも一方がラジカル重合性基を含む1価の有機基である、<2>に記載の樹脂組成物。
<4> 上記化合物Bが、式(1)で表される化合物を含む、<1>~<3>のいずれか1つに記載の樹脂組成物。
<5> 上記R1、R2及びR3のうち、少なくとも一つは重合性基を含む1価の有機基である、<4>に記載の樹脂組成物。
<6> 上記R1、R2及びR3のうち、少なくとも一つはラジカル重合性基である、<5>に記載の樹脂組成物。
<7> 光重合開始剤及び熱重合開始剤の少なくとも一方を更に含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 光重合開始剤を更に含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<9> 再配線層用層間絶縁膜の形成に用いられる、<1>~<8>のいずれか1つに記載の樹脂組成物。
<10> <1>~<9>のいずれか1つに記載の樹脂組成物を硬化してなる硬化物。
<11> <10>に記載の硬化物からなる層を2層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
<12> <1>~<9>のいずれか1つに記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。
<13> 上記膜を選択的に露光する露光工程及び上記膜を現像液を用いて現像してパターンを形成する現像工程を含む、<12>に記載の硬化物の製造方法。
<14> 上記膜を、50~450℃で加熱する加熱工程を含む、<12>又は<13>に記載の硬化物の製造方法。
<15> <10>に記載の硬化物又は<11>に記載の積層体を含む、半導体デバイス。
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。
本発明の樹脂組成物(以下、単に「樹脂組成物」ともいう。)は、ポリアミック酸エステルと、リン酸エステル、リン酸エステルアミド及びリン酸アミドよりなる群から選ばれる1種以上の化合物B(以下、単に「化合物B」ともいう)とを含む。
感光性を有する樹脂組成物である場合、ネガ型の樹脂組成物であってもポジ型の樹脂組成物であってもよいが、ネガ型の樹脂組成物であることが好ましい。
ネガ型の樹脂組成物とは、樹脂組成物から形成された層を露光した場合に、露光されていない部分(非露光部)が現像液により除去される組成物をいう。
ポジ型の樹脂組成物とは、樹脂組成物から形成された層を露光した場合に、露光された部分(露光部)が現像液により除去される組成物をいう。
本発明の樹脂組成物は、光重合開始剤及び熱重合開始剤の少なくとも一方を更に含むことが好ましく、光重合開始剤を更に含むことがより好ましい。
光重合開始剤を含むことにより、ネガ型の樹脂組成物として使用することができる。
また、熱重合開始剤を含むことにより、ネガ型の樹脂組成物、又は、ポジ型の樹脂組成物として使用することができる。
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。
本発明において、ポリアミック酸エステルとは、樹脂に含まれる全てのアミック酸構造及びアミック酸エステル構造の合計モル量に対する、アミック酸エステル構造の含有モル量の割合(%)が、50%以上である樹脂をいう。
上記含有モル量の割合(%)は、60%以上であることが好ましく、70%以上であることがより好ましく、80%以上であることが更に好ましく、90%以上であることが特に好ましい。上記含有モル量の割合(%)の上限は、特に限定されず、100%であってもよい。
このようなポリアミック酸エステルは、ポリアミック酸と比較して、分解反応により樹脂の主鎖が切断されて、樹脂が低分子量化されることが抑制されると推測される。そのため、本発明の樹脂組成物は、保存安定性に優れると考えられる。
また、化合物Bはポリアミック酸エステルと強く相互作用すると考えられる。この相互作用により、硬化前の膜(例えば、感光膜)の可塑性が向上し、硬化前の膜中での樹脂の部分構造の運動性が向上すると推測される。そのため、本発明の樹脂組成物からなる硬化前の膜を熱イミド化又は化学イミド化等によりイミド化した場合、ポリアミック酸エステルにおけるアミック酸エステル構造部分の運動性が向上し、イミド化しやすくなり、最終的に得られる硬化物におけるイミド化率が増加するため、耐薬品性に優れると推測される。
硬化物が耐薬品性に優れることにより、例えば、本発明の硬化性樹脂組成物を硬化してなる硬化物上に、溶剤を含む他の硬化性樹脂組成物を更に適用、硬化して積層体を作製する場合等に、硬化物が現像液又は他の硬化性樹脂組成物に接したとしても、硬化物の溶解が抑制されると考えられる。
本発明によれば、例えば、ジメチルスルホキシド(DMSO)、N-メチルピロリドン(NMP)等の極性溶剤、テトラメチルアンモニウムヒドロキシド(TMAH)水溶液等のアルカリ水溶液、又は、上記極性溶剤と上記アルカリ水溶液との混合液に対する溶解性が抑制された、耐薬品性に優れた硬化物が得られると考えられる。
更に、上記化合物B、及び、ポリアミック酸エステルの少なくとも一方にラジカル重合性基を導入すると、効率的に3次元架橋が形成され、耐薬品性はさらに向上すると考えられる。
また、上記硬化前の膜における可塑性の向上により、樹脂組成物が感光性を有する場合には、硬化前の膜における感光剤自体の構造変化及びそれにより引き起こされる重合性化合物の重合等の変化が起こりやすいため、解像性も向上すると推測される。
また、上記相互作用によるイミド化率の増加に起因して、本発明の樹脂組成物から得られる硬化物は、膜強度にも優れると推測される。
本発明の樹脂組成物は、ポリアミック酸エステル(以下、「特定樹脂」ともいう。)を含む。
また、ポリアミック酸エステルは、後述する式(2)で表される繰り返し単位を含むことが好ましい。
ポリアミック酸エステルにおける重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基等の公知の重合性基が挙げられる。
上記ラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
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等が挙げられ、(メタ)アクリロイルオキシ基が好ましい。
ポリアミック酸エステルがラジカル重合性基を有する場合、樹脂組成物は、感光剤として後述の光ラジカル重合開始剤を含むことが好ましく、感光剤として後述の光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く、感光剤として後述の光ラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような樹脂組成物からは、例えば、ネガ型感光層が形成される。
また、ポリアミック酸エステルは、酸分解性基等の極性変換基を有していてもよい。
ポリアミック酸エステルが酸分解性基を有する場合、樹脂組成物は、感光剤として後述の光酸発生剤を含むことが好ましい。このような樹脂組成物からは、例えば、化学増幅型であるポジ型感光層又はネガ型感光層が形成される。
本発明で用いるポリアミック酸エステルは、その種類等特に定めるものではないが、下記式(2)で表される繰り返し単位を含むことが好ましい。
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、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-又は-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。
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。
式中、*は他の構造との結合部位を表す。
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。
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。
例えば、R111は重合性基を有するジアミン化合物に由来する構造とすることもできる。
重合性基を有するジアミン化合物は、特に限定されないが、芳香環構造を含む化合物であることが好ましく、芳香環構造に、アミノ基及び重合性基を含む構造が直結した構造を有する化合物であることがより好ましい。
重合性基としては、エチレン性不飽和結合を有する基、環状エーテル基、メチロール基又はアルコキシメチル基を含む基が好ましく、ビニル基、(メタ)アリル基、(メタ)アクリルアミド基、(メタ)アクリロキシ基、マレイミド基、ビニルフェニル基、エポキシ基、オキセタニル基、メチロール基又はアルコキシメチル基がより好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、エポキシ基、メチロール基又はアルコキシメチル基が更に好ましい。
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。
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。
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。
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。
式(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。
上記ポリアミック酸エステル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。ポリアミック酸エステ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、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アミック酸エステルを含む場合、少なくとも1種のポリアミック酸エステ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、上記複数種のポリアミック酸エステルを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。
ポリアミック酸エステルは、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、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。
ポリアミック酸エステルの製造方法では、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。
ポリアミック酸エステルの製造方法では、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。
ポリアミック酸エステルの製造方法に際し、保存安定性をより向上させるため、ポリアミック酸エステル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。
ポリアミック酸エステルの製造に際し、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アミック酸エステル等を得ることができる。精製度を向上させるために、ポリアミック酸エステル等を再溶解、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。
本発明の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、本発明の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。
本発明の樹脂組成物は、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。
具体的には、本発明の樹脂組成物は、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。
本発明の樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリアミック酸エステルであって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリアミック酸エステルを含むことが好ましい。
本発明の樹脂組成物は、上述した特定樹脂と、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)とを含んでもよい。
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。
また、本発明の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、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い。
また、本発明の樹脂組成物の好ましい一態様として、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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、リン酸エステル、リン酸エステルアミド及びリン酸アミドよりなる群から選ばれる1種以上の化合物Bを含む。
本発明において、リン酸エステルアミドとは、リン酸エステル構造を少なくとも1つ有し、リン酸アミド構造を少なくとも1つ有する化合物をいう。
本発明において、リン酸アミドとは、リン酸アミド構造を少なくとも1つ有し、リン酸エステル構造を有しない化合物をいう。
化合物Bに含まれる重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基、アルコキシシリル基、ブロックイソシアネート基、オキサゾリル基等の公知の重合性基が挙げられ、ラジカル重合性基、エポキシ基又はアルコキシシリル基が好ましく、ラジカル重合性基がより好ましい。
上記ラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
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、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基等が挙げられ、(メタ)アクリロイルオキシ基が好ましい。
また、上記アルコキシシリル基としては、モノアルコキシシリル基、ジアルコキシシリル基、トリアルコキシシリル基のいずれでもよいが、ジアルコキシシリル基又はトリアルコキシシリル基が好ましく、トリアルコキシシリル基がより好ましい。
上記アルコキシシリル基におけるアルコキシの炭素数は、1~10であることが好ましく、1~4がより好ましく、1又は2が更に好ましく、2が特に好ましい。
化合物Bにおける重合性基の含有量は、0.0001~0.1mol/gであることが好ましく、0.001~0.01mol/gであることがより好ましい。
R1、R2及びR3は、重合性基を含まない1価の有機基、又は、重合性基を含む1価の有機基であることが好ましく、重合性基を含む1価の有機基であることが好ましい。
特に、R1、R2及びR3のうち、少なくとも1つが重合性基を含む1価の有機基であることが好ましく、少なくとも2つが重合性基を含む1価の有機基であることがより好ましく、3つ全てが重合性基を含む1価の有機基であることが更に好ましい。
R1、R2及びR3の少なくとも1つが重合性基を含む1価の有機基である場合、その重合性基の好ましい態様は、上述の化合物Bに含まれる重合性基の好ましい態様として記載したとおりである。
特に、R1、R2及びR3のうち、少なくとも2つがラジカル重合性基である態様が好ましく、少なくとも2つがラジカル重合性基である態様がより好ましく、少なくとも3つがラジカル重合性基である態様が更に好ましい。
また、R1、R2及びR3のうち、少なくとも2つが重合性基を含む1価の有機基である場合、これらの重合性基は同様であってもよいし異なっていてもよい。
重合性基を含む1価の有機基であるR1、R2又はR3は、下記式(P-1)で表される基であることが好ましい。
式(P-1)中、L1は単結合、又は、炭化水素基、エーテル結合、カルボニル基、チオエーテル結合、スルホニル基、-NRN-、若しくは、これらが2以上結合した基が好ましく、単結合、又は、炭化水素基、エーテル結合、カルボニル基、-NRN-、若しくは、これらが2以上結合した基がより好ましく、炭化水素基、又は、炭化水素基とエーテル結合の結合により表される基が更に好ましい。
上記RNは水素原子又は炭化水素基を表し、水素原子、アルキル基又はアリール基がより好ましく、水素原子又はアルキル基が更に好ましく、水素原子が特に好ましい。
上記L1における炭化水素基としては、炭素数1~30の飽和脂肪族炭化水素基、炭素数6~30の芳香族炭化水素基、又は、これらの組み合わせにより表される基が好ましく、炭素数1~10の飽和脂肪族炭化水素基、ベンゼン環から2以上の水素原子を除いた基、又は、これらの結合により表される基であることがより好ましい。
上記炭化水素基としては、アルキレン基、2価の芳香族炭化水素基、又はこれらの組み合わせにより表される基であることが好ましく、アルキレン基又はフェニレン基であることがより好ましい。
本明細書において、(ポリ)アルキレンオキシ基とは、アルキレンオキシ基又はポリアルキレンオキシ基を意味する。また、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。
上記アルキレン基としては、炭素数1~30のアルキレン基が好ましく、炭素数1~20のアルキレン基がより好ましく、炭素数1~10のアルキレン基が更に好ましい。
上記芳香族炭化水素基としては、炭素数6~30の芳香族炭化水素基が好ましく、炭素数6~20の芳香族炭化水素基がより好ましく、フェニレン基又はナフチレン基が更に好ましく、フェニレン基が特に好ましい。
上記(ポリ)アルキレンオキシ基におけるアルキレン基としては、炭素数2~10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く、エチレン基又はプロピレン基がより好ましく、エチレン基が更に好ましい。
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り返し数)は、2~20が好ましく、2~10がより好ましく、2~5が更に好ましく、2~4が特に好ましい。
式(1)中、耐薬品性の観点からは、X1、X2及びX3の少なくとも1つが-NRN-であることが好ましく、少なくとも2つが-NRN-であることがより好ましく、3つともが-NRN-であることが更に好ましい。
RNは水素原子又は炭素数1~20の1価の有機基を表すことが好ましく、水素原子又は炭素数1~20の炭化水素基を表すことがより好ましく、水素原子を表すことが更に好ましい。また、式中にRNが複数ある場合、これらのRNは同一であってもよいし異なっていてもよい。
下記化学式中、Etはエチル基を表し、nはそれぞれ独立に、繰り返し数を表し、2~10の整数が好ましい。
本発明の樹脂組成物は、化合物Bを1種単独で含んでもよいし、2種以上含んでもよい。
2種以上含む場合、その合計量が上述の範囲内となることが好ましい。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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。本発明の樹脂組成物は、光重合開始剤及び熱重合開始剤の少なくとも一方を含むことが好ましく、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。
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。
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。
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、ペンゾピラン系、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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
より好適には、少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。
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。
本発明の組成物は、熱酸発生剤を含んでもよい。
熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。
熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。
本発明の樹脂組成物は、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。本発明の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。
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。
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。
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。
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。
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。
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。
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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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。
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、本発明の樹脂組成物は、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。
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EO付加物ジメタリレート、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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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、本発明の樹脂組成物は、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。
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。
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。
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。
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。
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、モノジ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。
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。
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、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。
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。
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。
本発明の樹脂組成物は、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。
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。
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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物は、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。
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。
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、熱重合開始剤、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。
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。
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。
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。
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。
本発明の樹脂組成物は、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の樹脂組成物の表面に偏在させてもよい。
本発明の樹脂組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。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。熱ラジカル重合開始剤を添加することによって樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。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。
本発明の樹脂組成物は、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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
本発明の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、3,000mm2/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以下では、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困難であり、12,000mm2/s以上では、塗布面状が悪化する可能性がある。
本発明の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%以上では、樹脂組成物の保存安定性が損なわれる可能性がある。
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。
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。
本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が120℃~400℃の範囲内であることがより好ましく、140℃~380℃の範囲内にあることが更に好ましく、170℃~350℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物(硬化物からなる膜)の膜厚は、0.5μm以上150μm以下であることが好ましい。
本発明の樹脂組成物を硬化した際の収縮率は、50%以下が好ましく、45%以下がより好ましく、40%以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
収縮率[%]=100-(硬化後の体積÷硬化前の体積)×100
本発明の樹脂組成物の硬化物のイミド化反応率は、70%以上が好ましく、80%以上がより好ましく、90%以上が更に好ましい。70%未満では硬化物の機械特性が劣る可能性がある。
本発明の樹脂組成物の硬化物の破断伸びは、30%以上が好ましく、40%以上がより好ましく、50%以上が更に好ましい。
本発明の樹脂組成物の硬化物のガラス転移温度(Tg)は、180℃以上であることが好ましく、210℃以上であることがより好ましく、230℃以上であることがさらに好ましい。
本発明の樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
混合は撹拌羽による混合、ボールミルによる混合、タンク自身を回転させる混合などを採用することができる。
混合中の温度は10~30℃が好ましく、15~25℃がより好ましい。
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。
更にフィルターを用いたろ過後、ボトルに充填した樹脂組成物を減圧下に置き、脱気する工程を施しても良い。
本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含むことが好ましい。
また、本発明の硬化物の製造方法は、上記膜形成工程、膜形成工程により形成された膜を選択的に露光する露光工程、及び、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現像工程を含むことがより好ましい。
本発明の硬化物の製造方法は、上記膜形成工程、上記露光工程、上記現像工程、並びに、現像工程により得られたパターンを加熱する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。
また、本発明の製造方法は、上記膜形成工程、及び、上記膜を加熱する工程を含むことも好ましい。
以下、各工程の詳細について説明する。
本発明の樹脂組成物は、基材上に適用して膜を形成する膜形成工程に用いることができる。
本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含むことが好ましい。
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。
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。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。
上記膜は、膜形成工程(層形成工程)の後に、溶剤を除去するために形成された膜(層)を乾燥する工程(乾燥工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を乾燥する乾燥工程を含んでもよい。
また、上記乾燥工程は膜形成工程の後、露光工程の前に行われることが好ましい。
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。
上記膜は、膜を選択的に露光する露光工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を選択的に露光する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、本発明の樹脂組成物を硬化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。
また、露光に用いられる露光光が波長405nmの光を含むことも好ましい。
また、露光の方式は特に限定されず、本発明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。
上記膜は、露光後に加熱する工程(露光後加熱工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
露光後加熱工程は、露光工程後、現像工程前に行うことができる。
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。
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。
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。
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。
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現像工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、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。
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。
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。
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。
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。
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。
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、基材に液盛りによりリンス液を供給する方法、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、リンス液を上記露光後の膜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。
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加熱工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含んでもよい。
また、本発明の硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、膜形成工程により得られた膜を加熱する加熱工程を含んでもよい。
加熱工程において、ポリアミック酸エステル等の樹脂は環化してポリイミド等の樹脂となる。
また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
加熱工程における加熱温度(最高加熱温度)としては、50~450℃が好ましく、150~350℃がより好ましく、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。
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。
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。
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。
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。
現像工程により得られた(リンス工程を行う場合は、リンス後のパターン)は、上記加熱工程に代えて、又は、上記加熱工程に加えて、現像工程後のパターンを露光する現像後露光工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを露光する現像後露光工程を含んでもよい。本発明の硬化物の製造方法は、加熱工程及び現像後露光工程を含んでもよいし、加熱工程及び現像後露光工程の一方のみを含んでもよい。
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アミック酸エステル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。
現像後露光工程においては、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。
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有する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。
現像後露光工程は、例えば、上述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。
現像工程により得られたパターン(加熱工程及び露光後現像工程の少なくとも一方に供されたものが好ましい)は、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、本発明の硬化物の製造方法は、現像工程により得られたパターン(加熱工程及び現像後露光工程少なくとも一方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。
本発明の硬化物の製造方法、又は、本発明の硬化物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。
本発明の積層体とは、本発明の硬化物からなる層を複数層有する構造体をいう。
本発明の積層体は、硬化物からなる層を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層以上の上記硬化物からなる層のうち、少なくとも1つが本発明の硬化物からなる層であり、硬化物の収縮、又は、上記収縮に伴う硬化物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硬化物からなる層が本発明の硬化物からなる層であることも好ましい。
すなわち、本発明の積層体の製造方法は、複数回行われる硬化物の製造方法の間に、硬化物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、第一の硬化物からなる層、金属層、第二の硬化物からなる層の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。
上記第一の硬化物からなる層及び上記第二の硬化物からなる層は、いずれも本発明の硬化物からなる層であることが好ましい。上記第一の硬化物からなる層の形成に用いられる本発明の樹脂組成物と、上記第二の硬化物からなる層の形成に用いられる本発明の樹脂組成物とは、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。
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、パターン(樹脂層)又は金属層の表面に、再度、(a)膜形成工程(層形成工程)、(b)露光工程、(c)現像工程、(d)加熱工程及び現像後露光工程の少なくとも一方を、この順に行うことを含む一連の工程である。ただし、(a)の膜形成工程および(d)加熱工程及び現像後露光工程の少なくとも一方を繰り返す態様であってもよい。また、(d)加熱工程及び現像後露光工程の少なくとも一方の後には(e)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。
例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のように、樹脂層を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。
本発明の積層体の製造方法は、上記金属層および樹脂組成物層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、上記現像工程の後、樹脂組成物層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、露光後の樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の樹脂組成物層の両方について、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、表面に樹脂組成物層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樹脂組成物層(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、露光後の樹脂組成物層(樹脂層)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、樹脂組成物層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樹脂層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、樹脂組成物層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。
また、本発明は、本発明の硬化物、又は、本発明の積層体を含む半導体デバイスも開示する。
また、本発明は、本発明の硬化物の製造方法、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。本発明の樹脂組成物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。
〔オキシジフタル酸二無水物、ジエチレングリコールモノメチルエーテルおよび4,4’-ジアミノジフェニルエーテルからのポリアミック酸エステルA-1の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物20.0g(64.5ミリモル)をジグリム140ml中に懸濁させた。ジエチレングリコールモノメチルエーテル15.5g(129ミリモル)、ヒドロキノン0.05gおよびピリジン10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間攪拌した。 次いで、混合物を-20℃まで冷却した後、塩化チオニル16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温(25℃)まで温め、2時間攪拌した後、ピリジン9.7g(123ミリモル)およびN-メチルピロリドン(NMP)25mlを添加し、透明溶液を得た。次いで、4,4’-ジアミノジフェニルエーテル11.8g(58.7ミリモル)をNMP100ml中に溶解させ、上記透明溶液に1時間かけて滴下により添加した。4,4’-ジアミノジフェニルエーテルを添加している間、粘度が増加した。 次いで、混合物を2時間攪拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリアミック酸エステルA-1を得た。
得られたA-1の重量平均分子量(ゲルパーミエーションクロマトグラフィー(溶離液:NMP(N-メチル-2-ピロリドン)のポリスチレン換算値)は31000であった。
測定条件は以下の通りである。
カラム:TSKguardcolumn SuperAW-H(4.6mmID.×35mm)1本
TSK SuperAWM-H(6.0mmID.×150mm) 2本
展開溶媒:NMP(10mmol/L臭化リチウム、10mmol/Lリン酸溶液)
カラム温度:50℃
流量:0.35mL/分
サンプル注入量:20μL
サンプル濃度:0.1質量%
装置名:HLC-8220GPC(東ソー製)
検量線ベース樹脂:ポリスチレン
〔オキシジフタル酸二無水物、2-ヒドロキシエチルメタクリレートおよび4,4’-ジアミノジフェニルエーテルからのポリアミック酸エステルA-2の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物20.0g(64.5ミリモル)をジグリム140ml中に懸濁させた。2-ヒドロキシエチルメタクリレート16.8g(129ミリモル)、ヒドロキノン0.05gおよびピリジン10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間攪拌した。 次いで、混合物を-20℃まで冷却した後、塩化チオニル16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間攪拌した後、ピリジン9.7g(123ミリモル)およびN-メチルピロリドン(NMP)25mlを添加し、透明溶液を得た。次いで、4,4’-ジアミノジフェニルエーテル11.8g(58.7ミリモル)をNMP100ml中に溶解させ、上記透明溶液に1時間かけて滴下により添加した。4,4’-ジアミノジフェニルエーテルを添加している間、粘度が増加した。 次いで、混合物を2時間攪拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリアミック酸エステルA-2を得た。Mwは31000であった。
〔3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2-ヒドロキシエチルメタクリレートおよび4,4’-ジアミノジフェニルエーテルからのポリアミック酸エステルA-3の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物19.0g(64.5ミリモル)をジグリム140ml中に懸濁させた。2-ヒドロキシエチルメタクリレート16.8g(129ミリモル)、ヒドロキノン0.05gおよびピリジン10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間攪拌した。 次いで、混合物を-20℃まで冷却した後、塩化チオニル16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間攪拌した後、ピリジン9.7g(123ミリモル)およびN-メチルピロリドン(NMP)25mlを添加し、透明溶液を得た。次いで、4,4’-ジアミノジフェニルエーテル11.8g(58.7ミリモル)をNMP100ml中に溶解させ、上記透明溶液に1時間かけて滴下により添加した。4,4’-ジアミノジフェニルエーテルを添加している間、粘度が増加した。次いで、混合物を2時間攪拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリアミック酸エステルA-3を得た。Mwは31000であった。
〔オキシジフタル酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2-ヒドロキシエチルメタクリレートおよび4,4’-ジアミノジフェニルエーテルからのポリアミック酸エステルA-4の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物10.0g(32.2ミリモル)と3,3’,4,4’-ビフェニルテトラカルボン酸二無水物9.47g(32.3ミリモル)をジグリム140ml中に懸濁させた。2-ヒドロキシエチルメタクリレート16.8g(129ミリモル)、ヒドロキノン0.05gおよびピリジン10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間攪拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間攪拌した後、ピリジン9.7g(123ミリモル)およびN-メチルピロリドン(NMP)25mlを添加し、透明溶液を得た。次いで、4,4’-ジアミノジフェニルエーテル11.8g(58.7ミリモル)をNMP100ml中に溶解させ、上記透明溶液に1時間かけて滴下により添加した。4,4’-ジアミノジフェニルエーテルを添加している間、粘度が増加した。 次いで、混合物を2時間攪拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して除き、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリアミック酸エステルA-4を得た。Mwは30000であった。
〔オキシジフタル酸二無水物、2-ヒドロキシエチルメタクリレートおよび2,2’-ビス(トリフルオロメチル)ベンジジンからのポリアミック酸エステルA-5の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物20.0g(64.5ミリモル)をγ-ブチロラクトン55ml中に懸濁させた。2-ヒドロキシエチルメタクリレート16.8g(129ミリモル)、ヒドロキノン0.05gおよびピリジン10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間攪拌した。次いで、混合物を氷浴で冷却した後、ジシクロヘキシルカルボジイミド26.6g(129ミリモル)をγ-ブチロラクトン23mLに溶解した溶液を40分かけて加えた。次いで2,2’-ビス(トリフルオロメチル)ベンジジン18.8g(58.7ミリモル)とγ-ブチロラクトン45mlを混合した混合液を、反応溶液に1時間かけて添加した。次いで混合物を室温まで昇温し、2時間攪拌した後、エタノール2mLを加えて1時間撹拌し、γ‐ブチロラクトン50mLを加えた。次いで、反応混合物に生じた沈殿物を濾過により除き、500mLのエタノールの中で沈殿物を生成し、得られた沈殿物を濾別した後、テトラヒドロフラン250mLに溶解させた。得られた溶液を4リットルの水に滴下してポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を5000rpmの速度で15分間撹拌し、ポリイミド前駆体を濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリアミック酸エステルA-5を得た。Mwは30000であった。
〔オキシジフタル酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、および4,4’-ジアミノジフェニルエーテルからのポリアミック酸A-6の合成〕
攪拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で、4,4’-ジアミノジフェニルエーテル11.8g(58.7ミリモル)をNMP20gに溶解させた。次いで、オキシジフタル酸二無水物10.0g(32.2ミリモル)と3,3’,4,4’-ビフェニルテトラカルボン酸二無水物9.47g(32.3ミリモル)を加えた。60℃まで昇温し、3時間撹拌した後、室温まで冷却した。得られたポリイミド前駆体樹脂(ポリアミック酸A-6)をNMP溶液として得た。Mwは32000であった。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、テトラヒドロフラン(THF、200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルメタクリレート46.9g(360ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-1を45.3g(収率87%)得た。得られたB-1の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルメタクリレート31.2g(240ミリモル)、エタノール5.53g(120ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-2を35.7g(収率85%)得た。得られたB-2の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルメタクリレート15.6g(120ミリモル)、エタノール11.1g(240ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-3を26.5g(収率83%)得た。得られたB-3の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルアクリレート41.8g(360ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-4を42.3g(収率90%)得た。得られたB-4の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルメタクリレート31.2g(240ミリモル)を溶解させ、反応液に滴下した。30分後、さらに4-アミノスチレン14.3g(120ミリモル)を反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-5を41.7g(収率88%)得た。得られたB-5の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、ヒドロキシプロピルメタクリレート51.9g(360ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-6を52.0g(収率91%、異性体混合物)得た。得られたB-6の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
マグネチックスターラー、コンデンサーおよび内部温度計を取り付けた3つ口フラスコにオキシ塩化リン18.4g(120ミリモル)、THF(200mL)を加え、撹拌しながら氷冷した。次いで、THF200mLにトリエチルアミン20.2g(200ミリモル)、2-ヒドロキシエチルアクリルアミド41.4g(360ミリモル)を溶解させ、反応液に滴下した。30分後、室温まで昇温し、さらに30分撹拌した。不溶物を濾別し、ろ液に酢酸エチル1000mLを加え、有機相を1N(1mol/L)塩酸で洗浄した後、さらに水で3回洗浄した。有機相に硫酸マグネシウムを加えて乾燥させた後、不溶物を濾別し、ろ液に4-ヒドロキシ-TEMPO(0.05g)を加えて溶媒を減圧下留去することで、リン酸化合物B-7を42.3g(収率90%)得た。得られたB-7の構造は下記化学式により表される構造であることを、1H-NMRを用いて確認した。
各実施例において、それぞれ、下記表に記載の成分を混合し、各樹脂組成物を得た。また、各比較例において、それぞれ、下記表に記載の成分を混合し、各比較用組成物を得た。
具体的には、表に記載の溶剤以外の成分の含有量は、表の各「添加量」の欄に記載の量(質量部)とした。
なお、A-6については、溶液中の固形分量が表の各「添加量」に記載の量(質量部)となるように添加した。
得られた樹脂組成物及び比較用組成物を、細孔の幅が0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
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。
表中、「溶剤」以外の欄について、例えばA-2/A-3=50/50の記載は、A-2とA-3をA-2:50質量部、A-3:50質量部で含有させたことを示している。
表中、「溶剤」の欄について例えばNMP/EL=80/20の記載は、NMPとELをNMP:EL=80:20(質量比)で含有させたことを示している。また、「溶剤」の「添加量」の記載は、上記含有比の混合溶剤の合計含有量(質量部)を示している。
・A-1~A-6:上述の合成例で合成したA-1~A-6
・B-1~B-7:上記合成例で合成したB-1~B-7
・B-8:MR-200(大八化学工業製)
・B-9:MR-260(大八化学工業製)
・B-10:ホスマーM(ユニケミカル製)
・B-11:リン酸トリス(2-ブトキシエチル)
B-1~B-11はいずれも上述の化合物Bに該当する化合物である。
・NMP:N-メチルピロリドン
・EL:乳酸エチル
・GBL:γ-ブチロラクトン
・DMSO:ジメチルスルホキシド
<保存安定性の評価>
各実施例及び比較例において、それぞれ、調製した各樹脂組成物又は比較用組成物をスピンコート法でシリコンウエハ上に適用して熱硬化性樹脂組成物層を形成した。得られた熱硬化性樹脂組成物層を適用したシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に均一な約15μmの厚さの熱硬化性樹脂組成物層を得た。この値(15μm)を経時前膜厚とした。
〔経時後膜厚〕
各実施例及び比較例において、それぞれ、調製した各樹脂組成物又は比較用組成物をガラス容器に入れて密閉し、遮光、25℃の環境下に14日間静置した後、経時前膜厚を求めたときと同じ回転数を用いてスピンコート法でシリコンウエハ上に適用して熱硬化性樹脂組成物層を形成した。得られた熱硬化性樹脂組成物層を適用したシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に均一な熱硬化性樹脂組成物層を得た。得られた熱硬化性樹脂組成物層の膜厚を測定し、この値を経時後膜厚とした。基板上の樹脂組成物層の膜厚は光干渉式膜厚測定装置(大日本スクリーン製造(株)製ラムダエースVM-1030)を使用して測定した。なお、屈折率は、ポリイミドを対象に、1.629として測定した。
〔膜厚変化率〕
以下の式により、膜厚変化率を算出した。
膜厚変化率 (%) = |経時前膜厚-経時後膜厚|/経時前膜厚×100
膜厚変化率が10%未満をOK、10%以上をNGと判断した。評価結果は表中の「保存安定性」の欄に記載した。
各実施例及び比較例において、調製した各熱硬化性樹脂組成物又は比較用組成物をスピンコート法でシリコンウエハ上に適用して硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用したシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に約15μmの厚さの均一な熱硬化性樹脂組成物層を得た。組成物中に光重合開始剤を含有する例については、樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで全面露光した。組成物中に光重合開始剤を含有しない例においては、露光を行わなかった。得られた熱硬化性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度でボックスオーブンを用いて昇温し、表中の「硬化温度(℃)」に記載の温度に達した後、上記温度を3時間保持した。硬化後の樹脂層(硬化物)を4.9質量%フッ化水素酸溶液に浸漬し、シリコンウエハから硬化物を剥離した。剥離した硬化物を、打ち抜き機を用いて打ち抜いて、幅3mm、試料長30mmの試験片を作製した。得られた試験片を、引張り試験機(テンシロン)を用いて、クロスヘッドスピード300mm/分、フィルムの長手方向について、25℃、65%RH(相対湿度)の環境下にて、JIS-K6251:2017に準拠して測定した。評価は各5回ずつ実施し、フィルムが破断した時の伸び率(破断伸び率)について、上記5回の測定結果の算術平均値を指標値として用いた。
評価は下記基準に従って行い、評価結果は表中の「膜強度」の欄に記載した。破断伸び率(上記指標値)が大きいほど、膜強度が高いといえる。
-評価基準-
A 上記指標値が65%以上であった。
B 上記指標値が60%以上65%未満であった。
C 上記指標値が55%以上60%未満であった。
D 上記指標値が50%以上55%未満であった。
E 上記指標値が50%未満であった。
各実施例及び比較例において、調製した樹脂組成物又は比較用組成物を、それぞれ、スピンコート法でシリコンウエハ上に適用して硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用したシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に約15μmの厚さの均一な樹脂組成物層を得た。組成物中に光重合開始剤を含有する例については、樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで全面露光した。組成物中に光重合開始剤を含有しない例においては、露光を行わなかった。得られた樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表中の「硬化温度(℃)」に記載の温度に達した後、上記温度を3時間保持することで、シリコンウエハ上に硬化物を形成した。
硬化物をシリコンウエハから剥離せず、硬化物とシリコンウエハとを下記の薬液に下記の条件で浸漬し、溶解速度を算定した。
薬液:ジメチルスルホキシド(DMSO)と25質量%のテトラメチルアンモニウムヒドロキシド(TMAH)水溶液の90:10(質量比)の混合物
評価条件:薬液中に樹脂層を75℃で15分間浸漬して浸漬前後の膜厚を比較し、溶解速度(nm/分)を算出した。
評価は下記評価基準に従って行い、評価結果は表中の「耐薬品性」の欄に記載した。溶解速度が小さいほど、耐薬品性に優れるといえる。
-評価基準-
A 溶解速度が200nm/分未満であった。
B 溶解速度が200nm/分以上300nm/分未満であった。
C 溶解速度が300nm/分以上400nm/分未満であった。
D 溶解速度が400nm/分以上500nm/分未満であった。
E 溶解速度が500nm/分以上であった。
各実施例及び比較例において、調製した樹脂組成物又は比較用組成物を、それぞれ、スピンコート法でシリコンウエハ上に適用して樹脂組成物層を形成した。得られた樹脂組成物層を適用したシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に約15μmの厚さの均一な樹脂組成物層を得た。シリコンウエハ上の樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーでi線により露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が5から20μmまで1μm刻みの線幅が形成されたバイナリマスク)を介して行った。上記露光後、シクロペンタノンを用いて60秒間現像し、プロピレングリコールモノメチルエーテルアセテート(PGMEA)で20秒間リンスして、樹脂組成物層のラインアンドスペースパターンを得た。その後、得られた樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度でボックスオーブンを用いて昇温し、表中の「硬化温度(℃)」に記載の温度に達した後、上記温度を3時間保持することで、シリコンウエハ上にラインアンドスペースパターンの硬化物を形成した。得られたパターンを走査型電子顕微鏡を用い、倍率5000倍で観察し、残渣がなくラインアンドスペースパターンが解像している最小寸法を解像度とした。解像度が小さいほど、解像性に優れると言える。
なお、解像性の評価結果の欄に「-」と記載されている例については、解像性の評価を行わなかった。
-評価基準-
A 解像している最小寸法が7μm未満であった。
B 解像している最小寸法が7μm以上、10μm未満であった。
C 解像している最小寸法が10μm以上、15μm未満であった。
D 解像している最小寸法が15μm以上であった。
実施例1において、表中の「硬化温度(℃)」における加熱を行うための加熱手段を、ボックスオーブンから「赤外線ランプ加熱装置(アドバンス理工社製、RTP-6)」に変更した以外は、実施例1と同様の方法により、上述の膜強度、耐薬品性及び解像性の評価を行った。
具体的な加熱条件は、窒素雰囲気下で、10℃/分の昇温速度で昇温して、表中の「硬化温度(℃)」に記載の温度に達した後3時間その温度を保持する、という条件とした。
実施例51における膜強度、耐薬品性及び解像性の評価結果は、それぞれ、実施例1におけるこれらの評価結果と同様であった。
実施例22において、露光光源をステッパー(Nikon NSR 2005 i9C)からダイレクト露光装置(アドテック DE-6UH III)に変更した以外は、実施例22と同様の方法により解像性評価を行った。露光は波長405nmにおいて、露光部が線幅が5から20μmまでの1μm刻みの1:1ラインアンドスペースパターンにおけるライン部となるようなレーザーダイレクトイメージング露光を行った。露光量は500mJ/cm2とした。
実施例52における解像性の評価結果は、実施例22における解像性の評価結果と同様であった。
実施例22において、i線による露光を、波長405nmの光による露光へと変更した以外は、実施例22と同様の方法により、上述の膜強度、耐薬品性及び解像性の評価を行った。
実施例53における膜強度、耐薬品性及び解像性の評価結果は、それぞれ、実施例22におけるこれらの評価結果と同様であった。
比較例1~2に係る比較用組成物は化合物Bを含有しない。
このような比較用組成物から得られた硬化物は、耐薬品性に劣ることがわかる。
また、比較例3に係る樹脂組成物は、樹脂としてポリアミック酸エステルではなくポリアミック酸を用いている。このような比較用組成物は、保存安定性に劣ることがわかる。
実施例1において使用した樹脂組成物を、表面に銅薄層が形成された樹脂基材の表面にスピンコート法により層状に適用して、100℃で4分間乾燥し、膜厚20μmの樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノンで2分間現像し、PGMEAで30秒間リンスし、層のパターンを得た。
次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、230℃で3時間保持して、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。
Claims (15)
- ポリアミック酸エステルと、
リン酸エステル、リン酸エステルアミド及びリン酸アミドよりなる群から選ばれる1種以上の化合物Bとを含む
樹脂組成物。 - 式(2)における前記R113及びR114の少なくとも一方がラジカル重合性基を含む1価の有機基である、請求項2に記載の樹脂組成物。
- 前記R1、R2及びR3のうち、少なくとも一つは重合性基を含む1価の有機基である、請求項4に記載の樹脂組成物。
- 前記R1、R2及びR3のうち、少なくとも一つはラジカル重合性基である、請求項5に記載の樹脂組成物。
- 光重合開始剤及び熱重合開始剤の少なくとも一方を更に含む、請求項1~6のいずれか1項に記載の樹脂組成物。
- 光重合開始剤を更に含む、請求項1~6のいずれか1項に記載の樹脂組成物。
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~8のいずれか1項に記載の樹脂組成物。
- 請求項1~9のいずれか1項に記載の樹脂組成物を硬化してなる硬化物。
- 請求項10に記載の硬化物からなる層を2層以上含み、前記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
- 請求項1~9のいずれか1項に記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。
- 前記膜を選択的に露光する露光工程及び前記膜を現像液を用いて現像してパターンを形成する現像工程を含む、請求項12に記載の硬化物の製造方法。
- 前記膜を、50~450℃で加熱する加熱工程を含む、請求項12又は13に記載の硬化物の製造方法。
- 請求項10に記載の硬化物又は請求項11に記載の積層体を含む、半導体デバイス。
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WO2018225676A1 (ja) * | 2017-06-06 | 2018-12-13 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイスおよび化合物 |
WO2019146778A1 (ja) * | 2018-01-29 | 2019-08-01 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイス |
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