WO2020195993A1 - 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス - Google Patents
硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス Download PDFInfo
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- WO2020195993A1 WO2020195993A1 PCT/JP2020/011327 JP2020011327W WO2020195993A1 WO 2020195993 A1 WO2020195993 A1 WO 2020195993A1 JP 2020011327 W JP2020011327 W JP 2020011327W WO 2020195993 A1 WO2020195993 A1 WO 2020195993A1
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Classifications
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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
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
-
- 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
- C08F290/145—Polyamides; Polyesteramides; Polyimides
-
- 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
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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
- C08G73/22—Polybenzoxazoles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
- a resin obtained by cyclizing and curing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor").
- a polymer precursor such as a polyimide resin or a polybenzoxazole resin
- the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor”
- a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
- the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor.
- a curable resin composition is applied to a substrate by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the substrate.
- the curable 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 curable resin composition to be applied. It can be said that it has excellent adaptability.
- industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is expected more and more.
- Patent Document 1 contains a polyimide precursor, at least one resin of polyimide, and at least one urethane (meth) acrylate, and the urethane (meth) acrylate has a specific structure and is photosensitive.
- the sex resin composition is described.
- a curable resin composition obtained by curing a curable resin composition containing a heterocyclic-containing polymer precursor such as a polyimide precursor
- a curable resin composition is further applied on the cured film and cured to form a laminate.
- the cured film may come into contact with the developing solution or other composition. Therefore, in the curable resin composition, for example, from the viewpoint of resistance to a developing solution or suppression of dissolution due to contact with other compositions, a curable resin composition having excellent chemical resistance of the obtained cured film is provided. Is desired. Further, it is desired to provide a curable resin composition having excellent elongation at break in a cured film obtained by curing a curable resin composition containing a heterocyclic polymer precursor.
- a curable resin composition having excellent chemical resistance and elongation at break of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the production of the cured film It is an object of the method and a semiconductor device including the cured film or the laminate.
- the radically polymerizable group value derived from the compound having a radically polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 to 4.35 mmol / g. Curable resin composition.
- the polymerizable compound contains structure A, which is at least one structure selected from the group consisting of urethane bonds, urea bonds, and amide bonds, as a structure containing the hydrogen-bonding nitrogen atom.
- structure A which is at least one structure selected from the group consisting of urethane bonds, urea bonds, and amide bonds, as a structure containing the hydrogen-bonding nitrogen atom.
- ⁇ 3> The curable resin composition according to ⁇ 2>, wherein the polymerizable compound contains a structure B in which at least one binding site of the structure A and an alkylene group are directly bonded.
- ⁇ 4> At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and A polymerizable compound having a urea bond or an amide bond and having a group containing two or more ethylenically unsaturated groups.
- Curable resin composition. ⁇ 5> The curable resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerizable compound contains a (meth) acryloyl group as a group containing the ethylenically unsaturated group.
- ⁇ 6> The curable resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerizable compound has a molecular weight of 200 to 1,000.
- ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a photoradical polymerization initiator.
- ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising an onium salt or a thermobase generator.
- ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which contains a polyimide precursor as the polymer precursor.
- ⁇ 12> The curable resin composition according to any one of ⁇ 1> to ⁇ 11>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 13> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 14> A laminate containing two or more layers of the cured film according to ⁇ 13> and containing a metal layer between any of the cured films.
- ⁇ 15> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 12> to a substrate to form a film.
- ⁇ 16> The method for producing a cured film according to ⁇ 15>, which comprises an exposure step of exposing the film and a developing step of developing the film.
- ⁇ 17> The method for producing a cured film according to ⁇ 15> or ⁇ 16>, which comprises a heating step of heating the film at 50 to 450 ° C.
- a semiconductor device comprising the cured film according to ⁇ 13> or the laminate according to ⁇ 14>.
- a curable resin composition having excellent chemical resistance and elongation at break of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film.
- the semiconductor device including the cured film 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 desired 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 an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, 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
- (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 defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- GPC measurement 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 using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
- the opposite direction is referred to as "down”.
- the composition may contain, as each component contained in the composition, two or more kinds of 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 physical property values are values under the conditions of a temperature of 23 ° C. and an atmospheric pressure of 101,325 Pa (1 atm) unless otherwise specified.
- the combination of preferred embodiments is a more preferred embodiment.
- the curable resin composition is at least one polymer precursor (heterocycle-containing polymer) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
- a polymerizable compound (hereinafter, also referred to as “specific polymerizable compound 1”) having a hydrogen-bonding nitrogen atom and a group containing two or more ethylenically unsaturated groups.
- the radical polymerizable base value derived from the compound having a radically polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 to 4.35 mmol / g.
- the curable resin composition is at least one polymer precursor (heterocycle-containing polymer) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
- a precursor) and a polymerizable compound having a urea bond or an amide bond and having a group containing two or more ethylenically unsaturated groups hereinafter, also referred to as “specific polymerizable compound 2”. ..
- the curable resin composition according to the first aspect and the second aspect of the curable resin composition of the present invention may be collectively referred to as a "curable resin composition", and the specific polymerizable compound 1 and the specific polymerizable compound 1
- the compound 2 is also simply referred to as a "specific polymerizable compound”.
- the curable resin composition of the present invention preferably further contains a photoradical polymerization initiator described later.
- the curable resin composition of the present invention is excellent in chemical resistance and elongation at break of the obtained cured film.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- a curable resin composition containing a heterocyclic polymer precursor is heated, for example, a cured film containing a polyimide resin or a polybenzoxazole resin can be obtained by cyclization of the precursor.
- a compound having an ethylenically unsaturated group in order to improve the chemical resistance of the cured film.
- the radically polymerizable group value derived from the compound having a radically polymerizable group having a molecular weight of 2,000 or less is high (for example, 4.35 mmol / g) with respect to the total solid content of the composition.
- a conventional ethylenically unsaturated compound for example, in the case of curing at a low temperature of 200 ° C. or lower, the cyclization of the heterocyclic-containing polymer precursor is suppressed, which is obtained. It has been found that although the chemical resistance of the cured film is improved, the elongation at break is reduced.
- the present inventors use a specific polymerizable compound 1 having a hydrogen-bonding nitrogen atom and a double bond in the composition, and set the radical polymerizable base value to 0.25 to 4.35 mmol / g.
- the specific polymerizable compound 2 having a urea bond or an amide bond and having a group containing two or more ethylenically unsaturated groups, a cured film having excellent chemical resistance and elongation at break can be obtained. Found to be obtained.
- the curable resin composition of the present invention is lithography by using the specific polymerizable compound 2 having a radically polymerizable base value of 0.25 mol / g or more, or having a urea bond or an amide bond. It is thought that it is easy to be excellent in sex.
- Patent Document 1 includes a curable resin composition containing the specific polymerizable compound 1 and having a radically polymerizable base value of 0.25 to 4.35 mmol / g, and the specific polymerizable compound 2. There is no description or suggestion about the curable resin composition containing. Further, in the curable resin composition in Patent Document 1, there is room for further improvement in the chemical resistance of the cured film of the curable resin composition.
- the components contained in the curable resin composition of the present invention will be described in detail.
- the curable resin composition of the present invention contains a heterocyclic polymer precursor.
- the curable resin composition of the present invention contains, as the heterocyclic-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and includes a polyimide precursor. Is preferable.
- the polyimide precursor preferably has a repeating unit represented by the following formula (1).
- a 1 and A 2 each independently represent an oxygen atom or -NH-
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
- -A 1 and A 2- A 1 and A 2 in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.
- -R 111- R 111 in the formula (1) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified.
- the group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
- R 111 in formula (1) is preferably derived from diamine.
- diamine used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
- the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 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 or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
- the diamines (DA-1) to (DA-18) shown below are also preferable.
- a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example.
- a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
- Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
- EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
- x, y, and z are arithmetic mean values.
- R 111 in the formula (1) from the viewpoint of flexibility of the cured film obtained, -Ar 0 -L 0 -Ar 0 - is preferably represented by.
- Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
- the preferred range of L 0 is synonymous with A above.
- R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61).
- a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
- 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, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
- 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 independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
- Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
- -R 115- R 115 in the formula (1) 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.
- R 112 is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.
- tetravalent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
- the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
- R 115 represents a tetravalent organic group.
- R 115 has the same meaning as R 115 in formula (1).
- tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
- DAA-1 to DAA-5 tetracarboxylic dianhydrides
- DAA-5 tetracarboxylic dianhydrides
- R 113 and R 114- R 113 and R 114 in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group.
- the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group containing an ethylenically unsaturated bond.
- Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).
- R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
- R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
- ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
- the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
- R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2-, and more preferably ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- .
- R 200 is a methyl group and R 201 is an ethylene group.
- * represents a binding site with another structure.
- Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
- the acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
- a substituent that improves the solubility of the developing solution is preferably used.
- R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
- R 113 or R 114 is preferably a monovalent organic group.
- a monovalent organic group a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.
- the number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group).
- the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
- the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
- Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
- Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.
- aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
- the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
- the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran.
- Ring benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridin ring, acredin ring, phenanthrolin ring, thiantolen ring, chromium ring , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).
- the polyimide precursor has a fluorine atom in the repeating unit.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
- an aliphatic group having a siloxane structure may be copolymerized in a repeating unit represented by the formula (1).
- the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
- the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).
- a 11 and A 12 represent an oxygen atom or -NH-
- R 111 and R 112 each independently represent a divalent organic radical
- R 113 and R 114 independently represent a hydrogen atom or 1 Representing a valent organic group
- at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.
- a 11 , A 12 , R 111 , R 113 and R 114 are synonymous with the preferred ranges of A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), respectively.
- R 112 has the same meaning as R 112 in formula (5), and more preferably among others oxygen atoms.
- the bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.
- the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
- the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the degree of dispersion of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
- the polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
- the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
- the polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
- R 121 represents a divalent organic group.
- the divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable).
- the aromatic group constituting R 121 include R 111 of the above formula (1).
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same.
- R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
- R -R 123 and R 124- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
- the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
- the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
- SL diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s.
- Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s , and R 6s is aromatic.
- a group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms
- the rest are hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms).
- the a structure and the b structure may be block polymerization or random polymerization.
- the a structure is 5 to 95 mol%
- the b structure is 95 to 5 mol%
- a + b is 100 mol%.
- preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
- the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.
- the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more.
- the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass, based on the total solid content of the curable resin composition. The following is more preferable, 98% by mass or less is further preferable, 97% by mass or less is further preferable, and 95% by mass or less is further preferable.
- the curable resin composition of the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
- the composition is a polymerizable compound having a hydrogen-bonding nitrogen atom and having a group containing two or more ethylenically unsaturated groups (specifically.
- the radical polymerizable base value derived from the compound containing the polymerizable compound 1) and having a radically polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 to 4.35 mmol / g.
- the radical polymerizable group value derived from a compound having a radically polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is a radical polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition. It refers to the amount (mol amount) of ethylenically unsaturated groups contained in the compound having.
- the radically polymerizable group value can be calculated, for example, from structure determination by isolation of a compound having a radically polymerizable group having a molecular weight of 2,000 or less and measurement of the concentration in the composition by chromatography or the like. Measured by.
- the radically polymerizable base value is preferably 0.25 to 4.35 mmol / g, and more preferably 0.50 to 3.50 mol / g.
- Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 1 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is preferable, and from the viewpoint of reactivity, it is preferable. , (Meta) acryloyl groups are more preferred.
- the number of ethylenically unsaturated groups contained in the specific polymerizable compound 1 may be 2 or more, more preferably 2 to 8, and even more preferably 2 to 6.
- the molar amount (mol / g) of the ethylenically unsaturated group in 1 g of the specific polymerizable compound 1 is preferably 0.004 to 0.015 mol / g, and is 0.005 to 0.012 mol / g. Is more preferable.
- RN represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and even more preferably a hydrogen atom. If R N is more present in the molecule, a plurality of R N may be different or may be identical.
- the specific polymerizable compound 1 preferably contains a structure A, which is at least one structure selected from the group consisting of urethane bonds, urea bonds, and amide bonds, as a structure containing hydrogen-bonding nitrogen atoms.
- the specific polymerizable compound 1 preferably contains a urethane bond as a structure containing a hydrogen-bonding nitrogen atom, and from the viewpoint of improving chemical resistance, the specific polymerizable compound 1 has specific polymerizable properties.
- Compound 1 preferably contains at least one structure selected from the group consisting of urea bonds and amide bonds as a structure containing hydrogen-bonding nitrogen atoms.
- the number of hydrogen-bonding nitrogen atoms in the specific polymerizable compound 1 is preferably 2 to 6, and more preferably 2 to 4.
- the specific polymerizable compound 1 preferably contains a structure B in which at least one binding site of the structure A and an alkylene group are directly bonded.
- the alkylene group is preferably an alkylene group having 2 to 15 carbon atoms, and more preferably 2 to 10 alkylene groups.
- the alkylene group may be an alkylene group having a branched structure or a ring structure.
- the specific polymerizable compound 1 containing a urethane bond is preferably a compound represented by the following formula (UA-1) or formula (UA-2).
- (UA-1) or Formula (UA-2) L A1 represents a nA-valent linking group
- L A2 each independently represent a mA + 1 valent linking group
- R A1 is independently an ethylenically It represents a group containing an unsaturated group
- nA represents an integer of 2 or more
- mA represents an integer of 1 or more.
- L A1 is nA-valent is preferably a hydrocarbon group, nA-valent aliphatic saturated hydrocarbon group, nA-valent aromatic hydrocarbon group, or It is more preferable that the group has an nA value represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.
- R A1 is the vinyl group, an allyl group, a vinyl phenyl group, (meth) acrylamide group, or (meth) acryloxy groups are preferred, (meth) acryloxy group More preferred.
- nA represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2.
- the mA is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
- the specific polymerizable compound 1 containing a urea bond is preferably a compound represented by the following formula (UB-1).
- (UB-1) L B1 represents a nB valent linking group
- L B2 each independently represent an mB + 1 valent linking group
- R B1 is independently a group containing an ethylenically unsaturated group Represented
- nB represents an integer of 2 or more
- mB represents an integer of 1 or more.
- L B1 is nB titer is preferably a hydrocarbon group, nB-valent aliphatic saturated hydrocarbon group, nB valent aromatic hydrocarbon group, or an aliphatic saturated hydrocarbon group It is more preferable that the group has an nB valence represented by a combination of the aromatic hydrocarbon group and the aromatic hydrocarbon group.
- R B1 is a vinyl group, an allyl group, a vinyl phenyl group, (meth) acrylamide group, or (meth) acryloxy group, more preferably a (meth) acryloxy group.
- nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2.
- mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
- the specific polymerizable compound 1 containing an amide bond is a compound containing two or more structures represented by the following formula (AM-1) and a structure represented by the following formula (AM-2) in total. Is preferable.
- AM-1) and Formula (AM-2) R M1 represents a hydrogen atom or a methyl group
- R M2 represents a hydrogen atom or a hydrocarbon group
- * are each independently a bond with other structures Represents a part.
- RM1 is preferably a hydrogen atom.
- RM2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and even more preferably a hydrogen atom or a methyl group.
- Hydrogen atom is particularly preferable.
- the specific polymerizable compound 1 containing an amide group is preferably a compound represented by the following formula (AM-3).
- AM-3 R M1 represents a hydrogen atom or a methyl group
- R M2 represents a hydrogen atom or a hydrocarbon group
- L M1 represents n + 1 valent organic group
- n represents an integer of 1 or more
- N is 1
- LM1 has a group containing an ethylenically unsaturated group.
- RM1 is preferably a hydrogen atom.
- RM2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and even more preferably a hydrogen atom or a methyl group.
- Hydrogen atom is particularly preferable.
- RN is as described above.
- n is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4.
- L M1 has a group containing an ethylenically unsaturated group preferably contains a structure represented by the above formula (AM-2).
- the specific polymerizable compound 1 containing an amide group is a compound represented by the following formula (AM-4) or formula (AM-5). It is also preferable.
- (AM-4) or Formula (AM-5) L B1 represents a nB valent linking group
- L B2 each independently represent an mB + 1 valent linking group
- R B1 is independently ethylenically It represents a group containing an unsaturated group
- nB represents an integer of 2 or more
- mB represents an integer of 1 or more.
- L B1 is preferably an nB-valent hydrocarbon group, nB-valent aliphatic saturated hydrocarbon group, nB valent aromatic hydrocarbon group, or , It is more preferable that the group has an nB valence represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.
- R B1 is a vinyl group, an allyl group, a vinyl phenyl group, (meth) acrylamide group, or (meth) acryloxy groups are preferred, (meth) acryloxy group More preferred.
- nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. .
- the mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
- the molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 1 is preferably 200 to 1,000, more preferably 260 to 800, and further preferably 265 to 765. preferable.
- Specific examples of the specific polymerizable compound 1 include, but are not limited to, compounds having the following structures.
- the method for synthesizing the specific polymerizable compound 1 is not particularly limited, and it may be synthesized by a known method.
- the specific polymerizable compound 1 containing a urethane bond can be obtained, for example, by reacting a polyhydric isocyanate compound with a compound having a hydroxy group and an ethylenically unsaturated group. Further, as another synthesis method, for example, it can be obtained by reacting a polyhydric alcohol compound with a compound having an isocyanate group and an ethylenically unsaturated group.
- the specific polymerizable compound 1 containing a urea bond can be obtained, for example, by reacting a polyhydric isocyanate compound with a compound having an amino group and an ethylenically unsaturated group.
- the specific polymerizable compound 1 containing an amide bond can be obtained, for example, by reacting a polyvalent amine compound with an unsaturated carboxylic acid compound.
- it can be obtained by reacting a compound having an amino group and an ethylenically unsaturated group with a polyvalent carboxylic acid halide compound.
- the content of the specific polymerizable compound 1 is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the composition in the first aspect of the curable 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.
- the specific polymerizable compound 1 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.
- the composition is a polymerizable compound having a urea bond or an amide bond and having a group containing two or more ethylenically unsaturated groups (specific polymerization). Contains the sex compound 2).
- Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 2 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is preferable, and from the viewpoint of reactivity, it is preferable. , (Meta) acryloyl groups are more preferred.
- the number of ethylenically unsaturated groups contained in the specific polymerizable compound 2 may be 2 or more, more preferably 2 to 8, and even more preferably 2 to 6.
- the molar amount (mol / g) of the ethylenically unsaturated group in 1 g of the specific polymerizable compound 2 is preferably 0.004 to 0.015 mol / g, and is 0.005 to 0.012 mol / g. Is more preferable.
- Examples of the specific polymerizable compound 2 containing a urea bond include the same compounds as the above-mentioned specific polymerizable compound 1 containing a urea bond, and preferred embodiments and specific examples are also the same.
- Examples of the specific polymerizable compound 2 containing an amide bond include the same compounds as the above-mentioned specific polymerizable compound 1 containing an amide bond, and preferred embodiments and specific examples are also the same.
- the molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 2 is preferably 200 to 1,000, more preferably 200 to 800, and further preferably 260 to 600. preferable.
- the content of the specific polymerizable compound 2 is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the composition in the second aspect of the curable 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.
- the specific polymerizable compound 2 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.
- the radically polymerizable group value derived from the compound having a radically polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 mmol / g or more. It is preferably 0.50 mmol / g or more, and more preferably 0.50 mmol / g or more.
- the curable resin composition of the present invention preferably contains an onium salt.
- the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned. Among these, ammonium salt or iminium salt is preferable from the viewpoint of high thermal stability, and sulfonium salt, iodonium salt or phosphonium salt is preferable from the viewpoint of compatibility with the polymer.
- the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
- an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
- the onium salt used in the present invention may be a thermobase generator.
- the thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.
- ammonium salt means a salt of an ammonium cation and an anion.
- R 1 to R 4 independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
- R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
- R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
- the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
- the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
- R 101 represents an n-valent organic group
- R 1 has the same meaning as R 1 in the formula (101)
- Ar 101 and Ar 102 are each independently , Represents an aryl group
- n represents an integer of 1 or more.
- R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
- n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
- the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved.
- the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
- the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
- the stability, curability and developability of the curable resin composition can be further improved.
- the stability, curability and developability of the curable resin composition can be further improved.
- the carboxylic acid anion is preferably represented by the following formula (X1).
- EWG represents an electron-attracting group.
- the electron-attracting group means that the substituent constant ⁇ m of Hammett shows a positive value.
- ⁇ m is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
- the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
- R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
- the carboxylic acid anion is preferably represented by the following formula (XA).
- L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
- carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
- the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion from the viewpoint that the cyclization of the specific precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved. It is preferable to contain an anion having a pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
- the lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor or the like is improved. Is more preferable.
- the above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, FC See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using ACD / pKa (manufactured by ACD / Labs) software shall be used.
- ammonium salt examples include the following compounds, but the present invention is not limited thereto.
- the iminium salt means a salt of an iminium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- a pyridinium cation is preferable.
- a cation represented by the following formula (102) is also preferable.
- R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
- R 7 represents a hydrocarbon group
- at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
- R 5 and R 6 have the same meaning as R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
- R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
- the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
- the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
- R 101 represents an n-valent organic group
- R 5 has the same meaning as R 5 in the formula (102)
- R 7 is R in the formula (102) Synonymous with 7
- n and m represent integers of 1 or more.
- R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms.
- n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- iminium salt examples include the following compounds, but the present invention is not limited thereto.
- the sulfonium salt means a salt of a sulfonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
- R 8 to R 10 each independently represent a hydrocarbon group.
- Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
- Examples thereof include a carbonyl group and an acyloxy group.
- an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
- R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- sulfonium salt examples include the following compounds, but the present invention is not limited thereto.
- the iodonium salt means a salt of an iodonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- iodonium cation a diallyl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
- R 11 and R 12 each independently represent a hydrocarbon group.
- R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
- Examples thereof include a carbonyl group and an acyloxy group.
- R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- iodonium salt examples include the following compounds, but the present invention is not limited thereto.
- the phosphonium salt means a salt of a phosphonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
- R 13 to R 16 independently represent a hydrogen atom or a hydrocarbon group.
- Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
- Examples thereof include a carbonyl group and an acyloxy group.
- R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- phosphonium salt examples include the following compounds, but the present invention is not limited thereto.
- the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
- the onium salt 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 curable resin composition of the present invention may contain a thermal base generator.
- the thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
- examples of other thermobase generators include nonionic thermobase generators.
- Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
- 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 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 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 hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. 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 that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms). 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.
- a cyclohexyl group which may be used is more preferable.
- an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
- alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
- arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
- an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
- 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
- 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, further 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 effects of the present invention are 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 effects of the present invention are exhibited. Of these, 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). , 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), arylalkyl groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further 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, further preferably 3 to 8 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 is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is 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 have the same meanings as 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, further 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 are more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 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 12 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), 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.
- the molecular weight of the nonionic thermobase 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.
- the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.
- the content of the thermal base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
- the thermobase 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 curable resin composition of the present invention 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.
- a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
- 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 the range of about 300 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 as the photoradical polymerization initiator.
- 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.
- Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
- KayaCure DETX 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 also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
- IRGACURE 184 (IRGACURE is a registered trademark)
- DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
- the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
- acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
- metallocene compound examples include IRGACURE-784 (manufactured by BASF).
- An oxime compound is more preferable as the photoradical polymerization initiator.
- the exposure latitude can be improved more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-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 photopolymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
- the radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
- Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
- DFI-091 manufactured by Daito Chemix Corp.
- an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
- Examples of the most preferable oxime compound include 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.
- 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, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
- More preferable 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 trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more 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).
- 2-benzyl such as benzophenone
- 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.
- R I01 is a group represented by formula (II), the same as R I00
- the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
- 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 curable 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 is preferably in the above range.
- the curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
- a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.
- thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
- 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 curable resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains another polymerizable compound different from the above-mentioned specific polymerizable compound.
- the compound contained in the above-mentioned specific polymerizable compound shall not be contained in other polymerizable compounds.
- a radically polymerizable compound can be used as the other polymerizable compound.
- the radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
- the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
- the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
- the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
- the molecular weight of the radically polymerizable compound 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 radically polymerizable compound is preferably 100 or more.
- the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
- the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
- the radically polymerizable compound 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 preferred examples thereof. It is an ester of unsaturated carboxylic acid and polyhydric alcohol compound. Further, an addition reaction product of an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with a monofunctional or polyfunctional epoxy, or a monofunctional or polyfunctional carboxylic acid. The dehydration condensation reaction product of the above is also preferably used.
- Substitution reactions of unsaturated carboxylic acid esters having a desorbing substituent such as a group with monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like.
- 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.
- a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490.
- Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, 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 radically polymerizable compound 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. It is also possible to use a compound having two or more groups containing the above, or a cardo resin.
- the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
- radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku).
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 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, 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 ( Nippon 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.
- radically polymerizable compound compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.
- the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
- the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- a radically polymerizable compound having a group is more preferable.
- the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
- the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
- the acid value is measured according to the description of JIS K 0070: 1992.
- a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
- the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
- Acrylate derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
- the monofunctional radical polymerizable compound 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 curable resin composition of the present invention may further contain a polymerizable compound other than the above-mentioned radically polymerizable compound as the above-mentioned other polymerizable compound.
- a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
- R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
- R 105 is a group represented by -OR 106 or -OCO-R 107.
- R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 107 indicates an organic group having 1 to 10 carbon atoms.
- R 404 represents a divalent organic group having 1 to 200 carbon atoms
- R 405 represents a group represented by -OR 406 or -OCO-R 407
- R 406 is a hydrogen atom or carbon.
- R 407 indicates an organic group having 1 to 10 carbon atoms.
- U in the formula represents an integer of 3 to 8
- R 504 represents a u-valent organic group having 1 to 200 carbon atoms
- R 505 represents a group represented by -OR 506 or -OCO-R 507.
- R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 507 represents an organic group having 1 to 10 carbon atoms.
- Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
- Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
- HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
- 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 curable resin composition.
- 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; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi).
- epoxy groups include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
- an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
- Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain a polyethylene oxide group.
- 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.
- the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
- benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
- Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
- 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 curable 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 other polymerizable compound 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 in the above range.
- the curable 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, aromatic hydrocarbons, sulfoxides, and amides.
- esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
- Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
- 2-alkyloxy-2-methylpropionate etc.
- Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
- methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
- ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
- Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
- aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
- N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the mixed solvent to be mixed is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness and coating method.
- the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
- the curable 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 curable resin composition layer.
- the migration inhibitor is not particularly limited, but is a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- triazole-based compounds such as 1,2,4-triazole and benzotriazole
- tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole 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 rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
- 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 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 curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains a polymerization inhibitor.
- polymerization inhibitor examples include hydroquinone, 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-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
- the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.
- the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the curable 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 adhesiveness improving agent include a silane coupling agent.
- silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
- Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
- Et represents an ethyl group.
- the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
- the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
- the curable resin composition of the present invention contains various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired.
- additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired.
- Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended.
- the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
- the curable resin composition of the present invention may contain a sensitizer.
- the sensitizer absorbs specific active radiation and enters an electronically excited state.
- the sensitizer in the electron-excited state comes into contact with the thermal curing accelerator, 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 curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
- the sensitizer include sensitizers such as N-phenyldiethanolamine.
- the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the curable 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.
- As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- a thiol compound can be preferably used.
- the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
- 1 to 10 parts by mass is more preferable, and 1 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.
- Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
- the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
- the following surfactants are also preferable.
- the parentheses indicating the structural units of the main chain represent the content (mol%) of each structural unit
- the parentheses indicating the structural units of the side chain represent the number of repetitions of each structural unit.
- the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
- the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.
- the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
- a higher fatty acid derivative such as behenic acid or behenic acid amide
- the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
- the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
- the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
- a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
- Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
- the curable 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 more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. 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.
- a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
- a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.
- the curable resin composition of the present invention can be prepared by mixing the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used.
- the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the filter may be one that has been pre-cleaned with an organic solvent.
- a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times.
- circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- 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 curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
- the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
- the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
- the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
- Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- 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 may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
- the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.
- the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.
- the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
- the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C. Specifically, it is also preferable to include the following steps (a) to (d).
- A Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer)
- Exposure step of exposing the film after the film forming step
- Exposure Development step for developing the film
- Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. .. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
- the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
- the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after the cured film is formed according to the above-mentioned method for producing the cured film. )-(D).
- a laminated body can be obtained.
- the production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
- 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, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film) array substrates, and electrode plates of plasma display panels (PDPs).
- a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
- a plate-shaped base material (board) is used as the base material.
- the resin layer or the metal layer serves as a base material.
- Coating is preferable as a means for applying the curable resin composition to the base material.
- 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.
- the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
- a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, 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 2,000 rpm for about 10 seconds to 1 minute. It is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
- the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
- the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
- the preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
- the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
- the amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2 .
- the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
- the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
- the curable 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. As a result, particularly high exposure sensitivity can be obtained.
- the production method of the present invention may include a developing process step of performing a developing process (developing the film) on the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
- the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
- the developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent.
- the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
- the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
- Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)
- alkyl esters of 3-alkyloxypropionate eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-
- Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.
- aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene, etc.
- Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
- cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
- the developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
- the development time is preferably 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
- the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
- the rinsing time is preferably 5 seconds to 1 minute.
- the production method of the present invention preferably includes a heating step (heating step) of heating the developed film at 50 to 450 ° C.
- the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
- the heating step for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocyclic polymer precursor proceeds.
- curing of the specific polymerizable compound and other polymerizable compounds added as needed can also proceed in this step.
- the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C.
- the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
- the heating 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, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- 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 temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
- the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
- the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film.
- the ethynyl groups of the heterocyclic polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
- the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
- the pretreatment step is preferably 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.
- the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
- the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
- 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 performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the heterocyclic polymer precursor.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.
- metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. 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, and JP-A-2004-101850 can be used.
- photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
- the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest portion.
- the production method of the present invention preferably further includes a laminating step.
- the laminating step is a step of (a) film forming step (layer forming step), (b) exposure step, (c) developing process step, and (d) heating step again on the surface of the cured film (resin layer) or metal layer.
- the mode may be such that only the film forming step (a) is repeated.
- the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
- the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the drying step, the heating step, and the like as appropriate.
- the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
- An example of the surface activation treatment is plasma treatment.
- the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
- the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably 3 or more and 5 or less.
- a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
- Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
- the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
- the semiconductor device in which the curable 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 the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
- reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added.
- the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
- the obtained diester is chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor by the same method as in Synthesis Example 1. Obtained.
- the weight average molecular weight of this polyimide precursor was 18,000.
- ⁇ Synthesis example 4> [4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridine) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group) Synthesis of polyimide precursor)] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone.
- the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
- the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-5.
- the weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 20,000.
- Synthesis Example 6 [3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-7: Polyimide precursor having a radically polymerizable group) Body) synthesis]
- A-7 Polyimide precursor having a radically polymerizable group
- Synthesis Example 5 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid anhydride, in Synthesis Example 5.
- Polymer A-6 was obtained by carrying out the reaction in the same manner as described. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 22,000.
- the structures of the compounds C-1 to C-6 are the structures represented by the following formulas (C-1) to (C-6), respectively.
- the obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m.
- C C valence
- a radically polymerizable base value (mmol / g) derived from a compound having a radically polymerizable group having a molecular weight of 2,000 or less contained in the composition.
- the description of "-" indicates that the corresponding component is not contained.
- B-1 and B-2 Compounds with the following structure
- G-1 and G-2 Compounds with the following structures [Metal adhesion improver] -H-1 to H-3: Compounds having the following structures ⁇ solvent ⁇ -I-1: ⁇ -Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.) ⁇ I-2: Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) -I-3: N-methyl-2-pyrrolidone (manufactured by Ashland) ⁇ I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Other additives] ⁇ J-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
- a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin layer.
- the silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to obtain a uniform resin composition layer having a thickness of 20 ⁇ m on the silicon wafer.
- the resin composition layer on the silicon wafer was exposed to an exposure energy of 400 mJ / cm 2 using a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01), and the exposed resin composition layer was subjected to nitrogen.
- the temperature was raised at a heating rate of 5 ° C./min under an atmosphere, and after reaching 180 ° C., heating was performed for 2 hours.
- the heated resin composition layer and the silicon wafer were immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer.
- the peeled and heated resin composition layer was used as a cured film.
- the elongation at break was measured 10 times each, and the average value (the arithmetic mean value of the measured values of the elongation at break of a total of 10 by measuring 10 times in the longitudinal direction) was used.
- the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2. It can be said that the larger the value of the elongation at break, the better the elongation at break of the cured film.
- the curable resin composition or the comparative composition was spin-coated on a silicon wafer to form a resin layer.
- the silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to form a uniform resin composition layer having a film thickness of 20 ⁇ m on the silicon wafer.
- the resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) to obtain a resin composition layer after exposure. The exposure was performed using i-rays, and the exposure amount at a wavelength of 365 nm was 400 mJ / cm 2 .
- the exposure was performed using a photomask in which a line-and-space pattern was formed in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m.
- the resin composition layer after the exposure was developed with cyclopentanone for 60 seconds.
- the developed resin composition layer (line pattern) was observed using a scanning electron microscope (SEM) to determine the minimum line width.
- SEM scanning electron microscope
- the minimum line width is less than 10 ⁇ m
- B The minimum line width is 10 ⁇ m or more and less than 20 ⁇ m
- C The minimum line width is 20 ⁇ m or more, or a pattern having a line width with edge sharpness cannot be obtained. It was.
- a radically polymerizable base value derived from a compound having a heterocyclic-containing polymer precursor and a specific polymerizable compound 1 and having a radically polymerizable group having a molecular weight of 2,000 or less according to the present invention. It can be seen that the curable resin composition having a value of 0.25 to 4.35 mmol / g or the curable resin composition containing the specific polymerizable compound 2 is excellent in chemical resistance and elongation at break of the cured film.
- the curable resin compositions according to Comparative Examples 1 to 4 do not contain either the specific polymerizable compound 1 or the specific polymerizable compound 2.
- the curable resin compositions according to Comparative Examples 1 to 4 are inferior in the chemical resistance of the cured film.
- the curable resin composition according to Comparative Example 5 contains a specific polymerizable compound 1 and has a radical polymerizable base value of 4.35 mol / g derived from a compound having a radical polymerizable group having a molecular weight of 2,000 or less. Over. It can be seen that the curable resin composition according to Comparative Example 5 is inferior in elongation at break of the cured film.
- Example 101 The curable resin composition according to Example 1 is applied in layers to the surface of a resin base material on which a thin copper layer is formed by a spin coating method, dried at 100 ° C. for 5 minutes, and has a curability of a film thickness of 20 ⁇ m. After forming the resin composition layer, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern. Then, it was heated at 230 ° C.
- the interlayer insulating film for the rewiring layer was excellent in insulating properties. 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
そのため、硬化性樹脂組成物において、例えば、現像液への耐性又は他の組成物との接触による溶解の抑制等の観点から、得られる硬化膜の耐薬品性に優れる硬化性樹脂組成物の提供が望まれている。
また、複素環含有ポリマー前駆体を含む硬化性樹脂組成物を硬化してなる硬化膜において、破断伸びに優れた硬化性樹脂組成物の提供が望まれている。
<1> ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体、並びに、
水素結合性の窒素原子を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物を含み、
組成物の全固形分に対する、分子量2,000以下
のラジカル重合性基を有する化合物に由来するラジカル重合性基価が0.25~4.35mmol/gである、
硬化性樹脂組成物。
<2> 上記重合性化合物が、上記水素結合性の窒素原子を含む構造として、ウレタン結合、ウレア結合、及び、アミド結合よりなる群から選ばれた少なくとも一種の構造である構造Aを含む、<1>に記載の硬化性樹脂組成物。
<3> 上記重合性化合物が、上記構造Aの少なくとも一方の結合部位と、アルキレン基とが直接結合した構造である構造Bを含む、<2>に記載の硬化性樹脂組成物。
<4> ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体、並びに、
ウレア結合又はアミド結合を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物を含む、
硬化性樹脂組成物。
<5> 上記重合性化合物が、上記エチレン性不飽和基を含む基として、(メタ)アクリロイル基を含む、<1>~<4>のいずれか1つに記載の硬化性樹脂組成物。
<6> 上記重合性化合物の分子量が、200~1,000である、<1>~<5>のいずれか1つに記載の硬化性樹脂組成物。
<7> 光ラジカル重合開始剤を更に含む、<1>~<6>のいずれか1つに記載の硬化性樹脂組成物。
<8> オニウム塩又は熱塩基発生剤を更に含む、<1>~<7>のいずれか1つに記載の硬化性樹脂組成物。
<9> 上記ポリマー前駆体として、ポリイミド前駆体を含む、<1>~<8>のいずれか1つに記載の硬化性樹脂組成物。
<10> 上記ポリイミド前駆体が下記式(1)で表される繰返し単位を有する、<9>に記載の硬化性樹脂組成物;
<11> 上記式(1)におけるR113及びR114の少なくとも一方がラジカル重合性基を含む、<10>に記載の硬化性樹脂組成物。
<12> 再配線層用層間絶縁膜の形成に用いられる、<1>~<11>のいずれか1つに記載の硬化性樹脂組成物。
<13> <1>~<12>のいずれか1つに記載の硬化性樹脂組成物を硬化してなる硬化膜。
<14> <13>に記載の硬化膜を2層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
<15> <1>~<12>のいずれか1つに記載の硬化性樹脂組成物を基材に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<16> 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、<15>に記載の硬化膜の製造方法。
<17> 上記膜を50~450℃で加熱する加熱工程を含む、<15>又は<16>に記載の硬化膜の製造方法。
<18> <13>に記載の硬化膜又は<14>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測定)に従い、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、TSKgel Super HZ2000(東ソー(株)製)を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。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、感光層がある場合には、基材から感光層へ向かう方向を「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、物性値は、特に述べない限り、温度23℃及び気圧101,325Pa(1気圧)の条件下での値である。
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。
本発明の硬化性樹脂組成物の第一の態様において、硬化性樹脂組成物は、ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体(複素環含有ポリマー前駆体)、並びに、水素結合性の窒素原子を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物(以下、「特定重合性化合物1」ともいう。)を含み、組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価が0.25~4.35mmol/gである。
本発明の硬化性樹脂組成物の第二の態様において、硬化性樹脂組成物は、ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体(複素環含有ポリマー前駆体)、並びに、ウレア結合又はアミド結合を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物(以下、「特定重合性化合物2」ともいう。)を含む。
以下、本発明の硬化性樹脂組成物の第一の態様及び第二の態様における硬化性樹脂組成物を合わせて、単に「硬化性樹脂組成物」ともいい、特定重合性化合物1及び特定重合性化合物2を合わせて、単に「特定重合性化合物」ともいう。
また、本発明の硬化性樹脂組成物は、後述する光ラジカル重合開始剤を更に含むことが好ましい。
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。
複素環含有ポリマー前駆体を含む硬化性樹脂組成物を、例えば加熱した場合、前駆体の環化によりポリイミド樹脂又はポリベンゾオキサゾール樹脂を含む硬化膜が得られる。
ここで、硬化膜の耐薬品性を向上するために、エチレン性不飽和基を有する化合物をさらに導入することが考えられている。
しかし、本発明者らが鋭意検討した結果、組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価が高い(例えば4.35mmol/gを超える)場合など、従来のエチレン性不飽和化合物を用いた場合には、例えば200℃以下の低温での硬化においては、上記複素環含有ポリマー前駆体の環化が抑制されてしまい、得られる硬化膜において耐薬品性は向上するものの、破断伸びは低下してしまうことを見出した。
このように、得られる硬化膜において耐薬品性と破断伸びとを両立することは困難であった。
そこで本発明者らは、組成物に水素結合性の窒素原子及び二重結合を有する特定重合性化合物1を用い、かつ、上記ラジカル重合性基価を0.25~4.35mmol/gとするか、又は、ウレア結合若しくはアミド結合を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する特定重合性化合物2を用いることにより、耐薬品性及び破断伸びに優れる硬化膜が得られることを見出した。
これは、架橋後の特定重合性化合物同士、又は、架橋後の特定重合性化合物とポリイミド樹脂又はポリベンゾオキサゾール樹脂等が水素結合することにより、強固な膜が形成されるためであると推測される。
更に、本発明の硬化性樹脂組成物は、上記ラジカル重合性基基価が0.25mol/g以上であるか、又は、ウレア結合若しくはアミド結合を有する特定重合性化合物2を用いることにより、リソグラフィ性にも優れやすいと考えられる。
以下、本発明の硬化性樹脂組成物に含まれる成分について詳細に説明する。
本発明の硬化性樹脂組成物の第一の態様及び第二の態様において、組成物に含まれる特定重合性化合物以外の成分、及び、上記ラジカル重合性基価以外の組成又は物性、並びに、これらの好ましい態様は同様である。
本発明の硬化性樹脂組成物は、複素環含有ポリマー前駆体を含む。
本発明の硬化性樹脂組成物は、上記複素環含有ポリマー前駆体として、ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の前駆体を含み、ポリイミド前駆体を含むことが好ましい。
式(1)におけるA1及びA2は、それぞれ独立に、酸素原子又は-NH-を表し、酸素原子が好ましい。
式(1)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、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又はこれらを2以上組み合わせた基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基がより好ましい。
式(1)におけるR115は、4価の有機基を表す。4価の有機基としては、芳香環を含む4価の有機基が好ましく、下記式(5)又は式(6)で表される基がより好ましい。
式(1)におけるR113及びR114はそれぞれ独立に、水素原子又は1価の有機基を表す。R113及びR114の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を含む基が挙げられる。
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、1,2-ブタンジイル基、1,3-ブタンジイル基、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、-CH2CH(OH)CH2-が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CH2CH(OH)CH2-がより好ましい。
特に好ましくは、R200がメチル基で、R201がエチレン基である。
式(III)中、*は他の構造との結合部位を表す。
本発明におけるポリイミド前駆体の好ましい実施形態として、R113又はR114の1価の有機基として、1、2又は3つの、好ましくは1つの酸基を有する、脂肪族基、芳香族基及びアリールアルキル基などが挙げられる。具体的には、酸基を有する炭素数6~20の芳香族基、酸基を有する炭素数7~25のアリールアルキル基が挙げられる。より具体的には、酸基を有するフェニル基及び酸基を有するベンジル基が挙げられる。酸基は、ヒドロキシ基が好ましい。すなわち、R113又はR114はヒドロキシ基を有する基であることが好ましい。
R113又はR114が表す1価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。
本明細書において、分子量の分散度とは、重量平均分子量を数平均分子量により除した値(重量平均分子量/数平均分子量)をいう。
式(2)中、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基(炭素数1~24が好ましく、1~12がより好ましく、1~6が特に好ましい)及び芳香族基(炭素数6~22が好ましく、6~14がより好ましく、6~12が特に好ましい)の少なくとも一方を含む基が好ましい。R121を構成する芳香族基としては、上記式(1)のR111の例が挙げられる。上記脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、4,4’-オキシジベンゾイルクロリドに由来することが好ましい。
式(2)中、R122は、4価の有機基を表す。4価の有機基としては、上記式(1)におけるR115と同義であり、好ましい範囲も同様である。R122は、2,2'-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンに由来することが好ましい。
R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表し、上記式(1)におけるR113及びR114と同義であり、好ましい範囲も同様である。
本発明の硬化性樹脂組成物の第一の態様において、組成物は、水素結合性の窒素原子を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物(特定重合性化合物1)を含み、組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価が0.25~4.35mmol/gである。
組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価とは、組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に含まれるエチレン性不飽和基の量(mol量)をいう。
上記ラジカル重合性基価は、例えば、分子量2,000以下のラジカル重合性基を有する化合物の単離による構造決定とクロマトグラフィ等による組成物中の濃度測定とから算出することが可能である。
により測定される。
上記ラジカル重合性基価は、0.25~4.35mmol/gであることが好ましく、0.50~3.50mol/gであることがより好ましい。
特定重合性化合物1に含まれるエチレン性不飽和基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基等が挙げられ、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。
特定重合性化合物1に含まれるエチレン性不飽和基の数は、2つ以上であればよく、2~8であることがより好ましく、2~6であることが更に好ましい。
1gの特定重合性化合物1におけるエチレン性不飽和基のモル量(mol/g)は、0.004~0.015mol/gであることが好ましく、0.005~0.012mol/gであることがより好ましい。
特定重合性化合物1に含まれる水素結合性の窒素原子としては、特に限定されないが、ウレタン結合(-O-C(=O)-NRN-)、ウレア結合(-NRN-C(=O)-NRN-)、アミド結合(-C(=O)-NRN-)、アミノ基(-NRN-)、スルホンアミド結合(-S(=O)2NRN-)、含窒素複素環構造等に含まれる窒素原子が挙げられる。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好ましく、水素原子、炭素数1~4のアルキル基又はフェニル基がより好ましく、水素原子が更に好ましい。RNが分子中に複数存在する場合、複数のRNは同一であってもよいし異なっていてもよい。
特定重合性化合物1は、水素結合性の窒素原子を含む構造として、ウレタン結合、ウレア結合、及び、アミド結合よりなる群から選ばれた少なくとも一種の構造である構造Aを含むことが好ましい。
また、破断伸びを向上する観点からは、特定重合性化合物1は、水素結合性の窒素原子を含む構造として、ウレタン結合を含むことが好ましく、耐薬品性を向上する観点からは、特定重合性化合物1は、水素結合性の窒素原子を含む構造として、ウレア結合、及び、アミド結合よりなる群から選ばれた少なくとも一種の構造を含むことが好ましい。
特定重合性化合物1における水素結合性の窒素原子の数としては、2~6であることが好ましく、2~4であることがより好ましい。
上記アルキレン基は、炭素数2~15のアルキレン基であることが好ましく、2~10のアルキレン基であることがより好ましい。上記アルキレン基は、分岐構造又は環構造を有するアルキレン基であってもよい。
ウレタン結合を含む特定重合性化合物1は、下記式(UA-1)又は式(UA-2)により表される化合物であることが好ましい。
式(UA-1)又は式(UA-2)中、LA2は炭化水素基、エステル結合(-C(=O)O-)、エーテル結合(-O-)、カルボニル基(-C(=O)-)、ウレタン結合(-O-C(=O)-NRN-)、ウレア結合(-NRN-C(=O)-NRN-)、アミド結合(-C(=O)-NRN-)、アミノ基(-NRN-)、又は、これらを2以上組み合わせた基が好ましく、脂肪族飽和炭化水素基、芳香族炭化水素基、エステル結合、エーテル結合、又は、これらを2以上組み合わせた基がより好ましい。RNは上述した通りである。
式(UA-1)又は式(UA-2)中、RA1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、又は、(メタ)アクリロキシ基が好ましく、(メタ)アクリロキシ基がより好ましい。
式(UA-1)又は式(UA-2)中、nAは2以上の整数を表し、2~10が好ましく、2~6がより好ましく、2~4が更に好ましく、2が特に好ましい。
式(UA-1)又は式(UA-2)中、mAは1~10が好ましく、1~6がより好ましく、1~4が更に好ましく、1又は2が特に好ましく、1が最も好ましい。
ウレア結合を含む特定重合性化合物1は、下記式(UB-1)により表される化合物であることが好ましい。
式(UB-1)中、LB2は炭化水素基、エステル結合(-C(=O)O-)、エーテル結合(-O-)、カルボニル基(-C(=O)-)、ウレタン結合(-O-C(=O)-NRN-)、ウレア結合(-NRN-C(=O)-NRN-)、アミド結合(-C(=O)-NRN-)、アミノ基(-NRN-)、又は、これらを2以上組み合わせた基が好ましく、脂肪族飽和炭化水素基、芳香族炭化水素基、エステル結合、エーテル結合、又は、これらを2以上組み合わせた基がより好ましい。RNは上述した通りである。
式(UB-1)中、RB1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、又は、(メタ)アクリロキシ基が好ましく、(メタ)アクリロキシ基がより好ましい。
式(UB-1)中、nBは2以上の整数を表し、2~10が好ましく、2~6がより好ましく、2~4が更に好ましく、2が特に好ましい。
式(UB-1)中、mBは1~10が好ましく、1~6がより好ましく、1~4が更に好ましく、1又は2が特に好ましく、1が最も好ましい。
アミド結合を含む特定重合性化合物1は、下記式(AM-1)により表される構造及び下記式(AM-2)により表される構造の2種の構造を、合計で2つ以上含む化合物であることが好ましい。
式(AM-1)及び式(AM-2)中、RM1は水素原子が好ましい。
式(AM-1)中、RM2は水素原子、アルキル基又はアリール基が好ましく、水素原子、炭素数1~8のアルキル基、又は、フェニル基がより好ましく、水素原子又はメチル基が更に好ましく、水素原子が特に好ましい。
式(AM-3)中、RM1は水素原子が好ましい。
式(AM-3)中、RM2は水素原子、アルキル基又はアリール基が好ましく、水素原子、炭素数1~8のアルキル基、又は、フェニル基がより好ましく、水素原子又はメチル基が更に好ましく、水素原子が特に好ましい。
式(AM-3)中、LM1はn価の有機基を表し、炭化水素基、エステル結合(-C(=O)O-)、エーテル結合(-O-)、カルボニル基(-C(=O)-)、ウレタン結合(-O-C(=O)-NRN-)、ウレア結合(-NRN-C(=O)-NRN-)、アミド結合(-C(=O)-NRN-)、アミノ基(-NRN-)、上記式(AM-2)により表される構造、又は、これらを2以上組み合わせた基が好ましく、脂肪族飽和炭化水素基、芳香族炭化水素基、エステル結合、エーテル結合、上記式(AM-2)により表される構造、又は、これらを2以上組み合わせた基がより好ましい。RNは上述した通りである。
nは2~10が好ましく、2~6がより好ましく、2~4が更に好ましい。
nが1の場合、LM1はエチレン性不飽和基を含む基を有し、上記式(AM-2)により表される構造を含むことが好ましい。
式(AM-4)又は式(AM-5)中、LB2は炭化水素基、エステル結合(-C(=O)O-)、エーテル結合(-O-)、カルボニル基(-C(=O)-)、ウレタン結合(-O-C(=O)-NRN-)、ウレア結合(-NRN-C(=O)-NRN-)、アミド結合(-C(=O)-NRN-)、アミノ基(-NRN-)、又は、これらを2以上組み合わせた基が好ましく、脂肪族飽和炭化水素基、芳香族炭化水素基、エステル結合、エーテル結合、又は、これらを2以上組み合わせた基がより好ましい。RNは上述した通りである。
式(AM-4)又は式(AM-5)中、RB1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、又は、(メタ)アクリロキシ基が好ましく、(メタ)アクリロキシ基がより好ましい。
式(AM-4)又は式(AM-5)中、nBは2以上の整数を表し、2~10が好ましく、2~6がより好ましく、2~4が更に好ましく、2又は3が特に好ましい。
式(AM-4)又は式(AM-5)中、mBは1~10が好ましく、1~6がより好ましく、1~4が更に好ましく、1又は2が特に好ましく、1が最も好ましい。
特定重合性化合物1の分子量(分子量分布を有する場合は、重量平均分子量)は、200~1,000であることが好ましく、260~800であることがより好ましく、265~765であることが更に好ましい。
特定重合性化合物1の合成方法は特に限定されず、公知の方法により合成すればよい。
ウレタン結合を含む特定重合性化合物1は、例えば、多価イソシアネート化合物と、ヒドロキシ基及びエチレン性不飽和基を有する化合物と、を反応させることにより得ることができる。また、別の合成方法としては、例えば、多価アルコール化合物と、イソシアネート基及びエチレン性不飽和基を有する化合物と、を反応させることにより得ることができる。
ウレア結合を含む特定重合性化合物1は、例えば、多価イソシアネート化合物と、アミノ基及びエチレン性不飽和基を有する化合物と、を反応させることにより得ることができる。
アミド結合を含む特定重合性化合物1は、例えば、多価アミン化合物と、不飽和カルボン酸化合物との反応により得ることができる。また、別の合成方法としては、例えば、アミノ基及びエチレン性不飽和基を有する化合物と、多価カルボン酸ハライド化合物と、を反応させることにより得ることができる。
また、特定重合性化合物1としては、市販の化合物を使用してもよい。
特定重合性化合物1の含有量は、本発明の硬化性樹脂組成物の第一の態様における組成物の全固形分に対して、0質量%を超え60質量%以下であることが好ましい。下限は5質量%以上がより好ましい。上限は、50質量%以下であることがより好ましく、30質量%以下であることが更に好ましい。
特定重合性化合物1は1種を単独で用いてもよいが、2種以上を混合して用いてもよい。2種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。
本発明の硬化性樹脂組成物の第二の態様において、組成物は、ウレア結合又はアミド結合を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物(特定重合性化合物2)を含む。
特定重合性化合物2に含まれるエチレン性不飽和基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基等が挙げられ、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。
特定重合性化合物2に含まれるエチレン性不飽和基の数は、2つ以上であればよく、2~8であることがより好ましく、2~6であることが更に好ましい。
1gの特定重合性化合物2におけるエチレン性不飽和基のモル量(mol/g)は、0.004~0.015mol/gであることが好ましく、0.005~0.012mol/gであることがより好ましい。
特定重合性化合物2がウレア結合(-NRN-C(=O)-NRN-)を含む場合、特定重合性化合物2中のウレア結合の数は、1~10であることが好ましく、2~6であることがより好ましく、2~4であることが更に好ましい。RNは上述の通りである。
特定重合性化合物2がアミド結合(-NRN-C(=O)-)を含む場合、特定重合性化合物2中のアミド結合の数は、1~10であることが好ましく、2~6であることがより好ましく、2~4であることが更に好ましい。RNは上述の通りである。
アミド結合を含む特定重合性化合物2としては、上述のアミド結合を含む特定重合性化合物1と同様の化合物が挙げられ、好ましい態様及び具体例も同様である。
特定重合性化合物2の分子量(分子量分布を有する場合は、重量平均分子量)は、200~1,000であることが好ましく、200~800であることがより好ましく、260~600であることが更に好ましい。
特定重合性化合物2の含有量は、本発明の硬化性樹脂組成物の第二の態様における組成物の全固形分に対して、0質量%を超え60質量%以下であることが好ましい。下限は5質量%以上がより好ましい。上限は、50質量%以下であることがより好ましく、30質量%以下であることが更に好ましい。
特定重合性化合物2は1種を単独で用いてもよいが、2種以上を混合して用いてもよい。2種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。
組成物が特定重合性化合物2を含む場合の、組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価は、0.25mmol/g以上であることが好ましく、0.50mmol/g以上であることがより好ましい。
本発明の硬化性樹脂組成物は、オニウム塩を含むことが好ましい。
オニウム塩の種類等は特に定めるものではないが、アンモニウム塩、イミニウム塩、スルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましく挙げられる。
これらの中でも、熱安定性が高い観点からはアンモニウム塩又はイミニウム塩が好ましく、ポリマーとの相溶性の観点からはスルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましい。
すなわち、オニウム塩は、同一の分子構造内に、カチオン部と、アニオン部と、を有する分子内塩であってもよいし、それぞれ別分子であるカチオン分子と、アニオン分子と、がイオン結合した分子間塩であってもよいが、分子間塩であることが好ましい。また、本発明の硬化性樹脂組成物において、上記カチオン部又はカチオン分子と、上記アニオン部又はアニオン分子と、はイオン結合により結合されていてもよいし、解離していてもよい。
オニウム塩におけるカチオンとしては、アンモニウムカチオン、ピリジニウムカチオン、スルホニウムカチオン、ヨードニウムカチオン又はホスホニウムカチオンが好ましく、テトラアルキルアンモニウムカチオン、スルホニウムカチオン及びヨードニウムカチオンよりなる群から選択される少なくとも1種のカチオンがより好ましい。
熱塩基発生剤とは、加熱により塩基を発生する化合物をいい、例えば、40℃以上に加熱すると塩基を発生する酸性化合物等が挙げられる。
本発明において、アンモニウム塩とは、アンモニウムカチオンと、アニオンとの塩を意味する。
アンモニウムカチオンとしては、第四級アンモニウムカチオンが好ましい。
また、アンモニウムカチオンとしては、下記式(101)で表されるカチオンが好ましい。
R1~R4の少なくとも2つはそれぞれ結合して環を形成する場合、上記環はヘテロ原子を含んでもよい。上記ヘテロ原子としては、窒素原子が挙げられる。
式(Y1-1)において、R101は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からn個の水素原子を除いた基であることが好ましく、炭素数2~30の飽和脂肪族炭化水素、ベンゼン又はナフタレンからn個の水素原子を除いた基であることがより好ましい。
式(Y1-1)において、nは1~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
式(Y1-2)において、Ar101及びAr102はそれぞれ独立に、フェニル基又はナフチル基であることが好ましく、フェニル基がより好ましい。
アンモニウム塩におけるアニオンとしては、カルボン酸アニオン、フェノールアニオン、リン酸アニオン及び硫酸アニオンから選ばれる1種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
カルボン酸アニオンは、2個以上のカルボキシ基を持つ2価以上のカルボン酸のアニオンが好ましく、2価のカルボン酸のアニオンがより好ましい。この態様によれば、硬化性樹脂組成物の安定性、硬化性及び現像性をより向上できる。特に、2価のカルボン酸のアニオンを用いることで、硬化性樹脂組成物の安定性、硬化性及び現像性を更に向上できる。
σmが正の値を示す置換基の例としては、CF3基(σm=0.43)、CF3C(=O)基(σm=0.63)、HC≡C基(σm=0.21)、CH2=CH基(σm=0.06)、Ac基(σm=0.38)、MeOC(=O)基(σm=0.37)、MeC(=O)CH=CH基(σm=0.21)、PhC(=O)基(σm=0.34)、H2NC(=O)CH2基(σm=0.06)などが挙げられる。なお、Meはメチル基を表し、Acはアセチル基を表し、Phはフェニル基を表す(以下、同じ)。
上記pKaの下限は特に限定されないが、発生する塩基が中和されにくく、特定前駆体などの環化効率を良好にするという観点からは、-3以上であることが好ましく、-2以上であることがより好ましい。
上記pKaとしては、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値を用いることとする。
本発明において、イミニウム塩とは、イミニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。
式(102)中、R5及びR6は上述の式(101)におけるR1~R4と同義であり、好ましい態様も同様である。
式(102)中、R7はR5及びR6の少なくとも1つと結合して環を形成することが好ましい。上記環はヘテロ原子を含んでもよい。上記ヘテロ原子としては、窒素原子が挙げられる。また、上記環としてはピリジン環が好ましい。
式(Y1-3)において、R101は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からn個の水素原子を除いた基であることが好ましく、炭素数2~30の飽和脂肪族炭化水素、ベンゼン又はナフタレンからn個の水素原子を除いた基であることがより好ましい。
式(Y1-3)において、nは1~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
式(Y1-5)において、mは1~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
本発明において、スルホニウム塩とは、スルホニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。
スルホニウムカチオンとしては、第三級スルホニウムカチオンが好ましく、トリアリールスルホニウムカチオンがより好ましい。
また、スルホニウムカチオンとしては、下記式(103)で表されるカチオンが好ましい。
R8~R10はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R8~R10は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又は、アルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R8~R10は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。
本発明において、ヨードニウム塩とは、ヨードニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。
R11及びR12はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R11及びR12は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又はアルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R11及びR12は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。
本発明において、ホスホニウム塩とは、ホスホニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。
ホスホニウムカチオンとしては、第四級ホスホニウムカチオンが好ましく、テトラアルキルホスホニウムカチオン、トリアリールモノアルキルホスホニウムカチオン等が挙げられる。
また、ホスホニウムカチオンとしては、下記式(105)で表されるカチオンが好ましい。
R13~R16はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R13~R16は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又はアルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R13~R16は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。
オニウム塩は、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。
本発明の硬化性樹脂組成物は、熱塩基発生剤を含んでもよい。
熱塩基発生剤は、上述のオニウム塩に該当する化合物であってもよいし、上述のオニウム塩以外の他の熱塩基発生剤であってもよい。
他の熱塩基発生剤としては、ノニオン系熱塩基発生剤が挙げられる。
ノニオン系熱塩基発生剤としては、式(B1)又は式(B2)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、2~12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。
本発明の硬化性樹脂組成物は、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。
本発明の硬化性樹脂組成物は、重合開始剤として熱重合開始剤を含んでもよく、とく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、複素環含有ポリマー前駆体の環化と共に、複素環含有ポリマー前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
〔他のラジカル重合性化合物〕
本発明の硬化性樹脂組成物は、上述の特定重合性化合物とは異なる、他の重合性化合物を含むことが好ましい。
上述の特定重合性化合物に含まれる化合物は、他の重合性化合物には含まれないものとする。
他の重合性化合物としては、ラジカル重合性化合物を用いることができる。ラジカル重合性化合物は、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、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を含む基が挙げられる。ラジカル重合性基は、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。
本発明の硬化性樹脂組成物は、上記他の重合性化合物として、上述したラジカル重合性化合物以外の重合性化合物を更に含むことができる。上述したラジカル重合性化合物以外の重合性化合物としては、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;ベンゾオキサジン化合物が挙げられる。
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としては、下記式(AM1)、(AM4)又は(AM5)で示される化合物が好ましい。
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、硬化性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、OXT-191、OXT-223)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。
本発明の硬化性樹脂組成物は、溶剤を含有することが好ましい。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、芳香族炭化水素類、スルホキシド類、アミド類などの化合物が挙げられる。
本発明の硬化性樹脂組成物は、更にマイグレーション抑制剤を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硬化性樹脂組成物層内へ移動することを効果的に抑制可能となる。
本発明の硬化性樹脂組成物は、重合禁止剤を含むことが好ましい。
本発明の硬化性樹脂組成物は、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、シランカップリング剤などが挙げられる。
本発明の硬化性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱酸発生剤、N-フェニルジエタノールアミンなどの増感剤、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は硬化性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。
本発明の硬化性樹脂組成物は、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、熱硬化促進剤、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、熱硬化促進剤、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。
増感剤としては、N-フェニルジエタノールアミン等の増感剤が挙げられる。
また、増感剤としては、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。
本発明の硬化性樹脂組成物は、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SH、PH、SiH、及びGeHを有する化合物群が用いられる。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。
本発明の硬化性樹脂組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。下記式中、主鎖の構成単位を示す括弧は各構成単位の含有量(モル%)を、側鎖の構成単位を示す括弧は各構成単位の繰り返し数をそれぞれ表す。
本発明の硬化性樹脂組成物は、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硬化性樹脂組成物の表面に偏在させてもよい。
本発明の硬化性樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がより好ましく、0.6質量%未満が更に好ましい。
本発明の硬化性樹脂組成物は、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。
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。
本発明の硬化性樹脂組成物は、再配線層用層間絶縁膜の形成に用いられることが好ましい。
また、その他、半導体デバイスの絶縁膜の形成、又は、ストレスバッファ膜の形成等にも用いることができる。
次に、硬化膜、積層体、半導体デバイス、及びそれらの製造方法について説明する。
本発明の硬化膜の製造方法は、上記膜形成工程、並びに、上記膜を露光する露光工程及び上記膜を現像する現像工程を含むことが好ましい。
また、本発明の硬化膜の製造方法は、上記膜形成工程、及び、必要に応じて上記現像工程を含み、かつ、上記膜を50~450℃で加熱する加熱工程を含むことがより好ましい。
具体的には、以下の(a)~(d)の工程を含むことも好ましい。
(a)硬化性樹脂組成物を基材に適用して膜(硬化性樹脂組成物層)を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された上記膜を現像する現像工程
(d)現像された上記膜を50~450℃で加熱する加熱する加熱工程
上記加熱工程において加熱することにより、露光で硬化した樹脂層を更に硬化させることができる。この加熱工程で、例えば上述の熱塩基発生剤が分解し、十分な硬化性が得られる。
<膜形成工程(層形成工程)>
本発明の好ましい実施形態に係る製造方法は、硬化性樹脂組成物を基材に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。
また、基材としては、例えば板状の基材(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。
本発明の製造方法は、上記膜(硬化性樹脂組成物層)を形成後、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。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、3分~7分がより好ましい。
本発明の製造方法は、上記膜(硬化性樹脂組成物層)を露光する露光工程を含んでもよい。露光量は、硬化性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100~10,000mJ/cm2照射することが好ましく、200~8,000mJ/cm2照射することがより好ましい。
本発明の製造方法は、露光された膜(硬化性樹脂組成物層)に対して、現像処理を行う(上記膜を現像する)現像処理工程を含んでもよい。現像を行うことにより、露光されていない部分(非露光部)が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えば、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。
本発明の製造方法は、現像された上記膜を50~450℃で加熱する加熱する工程(加熱工程)を含むことが好ましい。
加熱工程は、膜形成工程(層形成工程)、乾燥工程、及び現像工程の後に含まれることが好ましい。加熱工程では、例えば上述の熱塩基発生剤が分解することにより塩基が発生し、複素環含有ポリマー前駆体の環化反応が進行する。また、特定重合性化合物及び必要に応じて添加される他の重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることが更に好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることが更に一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることが更に好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。
本発明の製造方法は、現像処理後の膜(硬化性樹脂組成物層)の表面に金属層を形成する金属層形成工程を含んでいることが好ましい。
本発明の製造方法は、更に、積層工程を含むことが好ましい。
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテル及びベンジルアルコールからのポリイミド前駆体(A-1:ラジカル重合性基を有さないポリイミド前駆体)の合成〕
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥)と、14.22g(131.58ミリモル)のベンジルアルコールを、50mLのN-メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を100℃で3時間加熱した。反応混合物を室温に冷却し、21.43g(270.9ミリモル)のピリジン及び90mLのN-メチルピロリドンを加えた。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-5~0℃で20分かけて反応混合物に滴下した。次いで、反応混合物を0℃で1時間反応させたのち、エタノールを70g加えて、室温で1晩撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpmの速度で15分間撹拌した。ポリイミド前駆体をろ過して除き、4リットルの水の中で再度30分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥した。このポリイミド前駆体の重量平均分子量は、18,000であった。
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2:ラジカル重合性基を有するポリイミド前駆体)の合成〕
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライム(ジエチレングリコールジメチルエーテル)を混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-3:ラジカル重合性基を有するポリイミド前駆体)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、18,000であった。
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-4:ラジカル重合性基を有するポリイミド前駆体)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-5:ラジカル重合性基を有するポリイミド前駆体)の合成〕
4,4’-オキシジフタル酸無水物(ODPA)155.1gを2リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)134.0g及びγ―ブチロラクトン400mlを加えた。室温下で撹拌しながら、ピリジン79.1gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。
〔3,3’4,4’-ビフェニルテトラカルボン酸二無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-7:ラジカル重合性基を有するポリイミド前駆体)の合成〕
合成例5において、4,4’-オキシジフタル酸無水物155.1gに代えて、3,3’4,4’-ビフェニルテトラカルボン酸二無水物147.1gを用いた以外は、合成例5に記載の方法と同様にして反応を行うことにより、ポリマーA-6を得た。このポリマーA-6の重量平均分子量(Mw)を測定したところ、22,000であった。
〔化合物C-1の合成〕
30~90℃に加温したヘキサメチレンジイソシアネートとジブチル錫ジラウレート等の触媒との混合物中に、ライトアクリレートPE-3A(共栄社化学株式会社)を滴下して、6~12時間反応させることにより、化合物C-1を合成した。
〔化合物C-2の合成〕
化合物C-1の合成において、ヘキサメチレンジイソシアネートをイソホロン時イソシアネートに変更した以外は、化合物C-1の合成と同様の方法により化合物C-2を合成した。
〔化合物C-3の合成〕
氷冷下、カレンズBEI(昭和電工(株)製)にp-キシレンジアミンを滴下し、室温にて6~12時間反応させることにより、化合物C-3を合成した。
〔化合物C-4の合成〕
特開2012-206992号公報に記載の合成方法を参考に、化合物C-4を合成した。
〔化合物C-5の合成〕
30~90℃に加温したカレンズMOIとジブチル錫ジラウレート等の触媒との混合物中に、1,2,4-ブタントリオールを滴下して、6~12時間反応させることにより化合物C-5を合成した。
〔化合物C-6の合成〕
氷冷下、1,3,5-ベンゼントリカルボン酸にメタクリル酸2-アミノエチル塩酸塩を滴下し、室温にて6~12時間反応させることにより、化合物C-6を合成した。
各実施例において、それぞれ、下記表1に記載の成分を混合し、各硬化性樹脂組成物を得た。また、各比較例において、それぞれ、下記表1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1の「溶剤」以外の欄に記載の成分の含有量は、表1の「質量部」に記載の量とし、表1の「溶剤」の欄に記載の成分の含有量は、組成物の固形分濃度が表1に記載の値となる量とした。
また、表1の「溶剤」の「I-1/I-2」「80/20」の記載は、I-1とI-2の含有量の比が、質量比でI-1:I-2=80:20であることを示している。
得られた硬化性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。
表1中、「C=C価」の欄の記載は、組成物に含まれる、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価(mmol/g)を表している。
また、表1中、「-」の記載は該当する成分を含有していないことを示している。
・A-1~A-6:上記で合成したA-1~A-6
・C-1~C-6:上述の合成例で得られた化合物
・G-1及びG-2:下記構造の化合物
・H-1~H-3:下記構造の化合物
・I-1:γ-ブチロラクトン(三和油化社製)
・I-2:ジメチルスルホキシド(富士フイルム和光純薬(株)製)
・I-3:N-メチル-2-ピロリドン(Ashland社製)
・I-4:乳酸エチル(東京化成工業(株)製)
〔その他の添加剤〕
・J-1:N-フェニルジエタノールアミン(東京化成工業(株)製)
各実施例及び比較例において、それぞれ、硬化性樹脂組成物又は比較用組成物をシリコンウェハ上にスピンコート法により適用し、樹脂層を形成した。上記樹脂層が形成されたシリコンウェハをホットプレート上で、100℃で4分間乾燥し、シリコンウェハ上に20μmの厚さの均一な樹脂組成物層とした。
シリコンウェハ上の樹脂組成物層を、ブロードバンド露光機(ウシオ電機株式会社製:UX-1000SN-EH01)を用いて、400mJ/cm2の露光エネルギーで露光し、露光した樹脂組成物層を、窒素雰囲気下で、5℃/分の昇温速度で昇温し、180℃に達した後、2時間加熱した。上記加熱後の樹脂組成物層及びシリコンウェハを3質量%フッ化水素酸水溶液に浸漬し、シリコンウェハから加熱後の樹脂組成物層を剥離した。上記剥離した加熱後の樹脂組成物層を硬化膜とした。
各実施例及び比較例において、それぞれ、得られた上記硬化膜を用いて、耐薬品性、破断伸び率、及び、解像性の評価を行った。
各評価における評価方法の詳細を下記に記載する。
得られた硬化膜について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:薬液中に硬化膜を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。膜厚は光学式の膜厚計(Footfill社製、KT-22)を用いて測定した。
評価は下記評価基準に従って行い、評価結果は表2に記載した。溶解速度の値が小さいほど、硬化膜は耐薬品性に優れるといえる。
A:溶解速度が250nm/分未満であった。
B:溶解速度が250nm/分以上350nm/分未満であった。
C:溶解速度が350nm/分以上450nm/分未満であった。
D:溶解速度が450nm/分以上であった。
得られた硬化膜の破断伸び率を測定した。硬化膜の破断伸び率は、引張り試験機(テンシロン)を用い、クロスヘッドスピード300mm/分、試料幅10mm、試料長50mmとして、フィルムの長手方向及び幅方向について、25℃、65%RH(相対湿度)の環境下にて、JIS-K6251(日本工業規格)に準拠して測定した。破断伸び率は、Eb(%)=(Lb-L0)/L0(Eb:破断伸び率、L0:試験前の試験片の長さ、Lb:試験片が切断した時の試験片の長さ)で算出した。評価は破断伸び率を各10回ずつ測定し、平均値(長手方向10回の測定による、計10個の破断伸び率の測定値の算術平均値)を用いた。
評価は下記評価基準に従って行い、評価結果は表2に記載した。破断伸び率の値が大きいほど、硬化膜は破断伸び率に優れるといえる。
A:上記平均値が60%以上である
B:上記平均値が50%以上60%未満である
C:上記平均値が45%以上50%未満である
D:上記平均値が45%未満である
各実施例及び比較例において、それぞれ、硬化性樹脂組成物又は比較用組成物を、シリコンウェハ上にスピンコートし、樹脂層を形成した。上記樹脂層が形成されたシリコンウェハをホットプレート上で、100℃で4分間乾燥し、シリコンウェハ上に20μmの膜厚の均一な樹脂組成物層を形成した。シリコンウェハ上の樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて露光し、露光後の樹脂組成物層を得た。露光はi線を用いて行い、波長365nmにおける露光量を400mJ/cm2とした。また、露光は5μmから25μmまで1μm刻みのラインアンドスペースパターンが形成されたフォトマスクを使用して行った。上記露光後の樹脂組成物層を、シクロペンタノンを用いて60秒間現像した。
上記現像後の樹脂組成物層(ラインパターン)を、走査型電子顕微鏡(SEM)を用いて観察し、最小線幅を決定した。
評価は下記評価基準に従って行い、評価結果は表2に記載した。上記最小線幅が小さいほどリソグラフィ性(解像性)に優れるといえる。
A:最小線幅が10μm未満である
B:最小線幅が10μm以上20μm未満である
C:最小線幅が20μm以上であるか、又は、エッジの鋭さを持つ線幅を有するパターンが得られなかった。
比較例1~4に係る硬化性樹脂組成物は、特定重合性化合物1及び特定重合性化合物2のいずれも含有しない。この比較例1~4に係る硬化性樹脂組成物は、硬化膜の耐薬品性に劣ることが分かる。
比較例5に係る硬化性樹脂組成物は、特定重合性化合物1を含有するが、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価が4.35mol/gを超えている。この比較例5に係る硬化性樹脂組成物は、硬化膜の破断伸びに劣ることが分かる。
実施例1に記載の硬化性樹脂組成物を、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5分間乾燥し、膜厚20μmの硬化性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。露光の後、シクロペンタノンで30秒間現像し、PGMEAで20秒間リンスし、パターンを得た。
次いで、230℃で3時間加熱し、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 (18)
- ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体、並びに、
水素結合性の窒素原子を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物を含み、
組成物の全固形分に対する、分子量2,000以下のラジカル重合性基を有する化合物に由来するラジカル重合性基価が0.25~4.35mmol/gである、
硬化性樹脂組成物。 - 前記重合性化合物が、前記水素結合性の窒素原子を含む構造として、ウレタン結合、ウレア結合、及び、アミド結合よりなる群から選ばれた少なくとも一種の構造である構造Aを含む、請求項1に記載の硬化性樹脂組成物。
- 前記重合性化合物が、前記構造Aの少なくとも一方の結合部位と、アルキレン基とが直接結合した構造である構造Bを含む、請求項2に記載の硬化性樹脂組成物。
- ポリイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選択された少なくとも1種のポリマー前駆体、並びに、
ウレア結合又はアミド結合を有し、かつ、2つ以上のエチレン性不飽和基を含む基を有する重合性化合物を含む、
硬化性樹脂組成物。 - 前記重合性化合物が、前記エチレン性不飽和基を含む基として、(メタ)アクリロイル基を含む、請求項1~4のいずれか1項に記載の硬化性樹脂組成物。
- 前記重合性化合物の分子量が、200~1,000である、請求項1~5のいずれか1項に記載の硬化性樹脂組成物。
- 光ラジカル重合開始剤を更に含む、請求項1~6のいずれか1項に記載の硬化性樹脂組成物。
- オニウム塩又は熱塩基発生剤を更に含む、請求項1~7のいずれか1項に記載の硬化性樹脂組成物。
- 前記ポリマー前駆体として、ポリイミド前駆体を含む、請求項1~8のいずれか1項に記載の硬化性樹脂組成物。
- 前記式(1)におけるR113及びR114の少なくとも一方がラジカル重合性基を含む、請求項10に記載の硬化性樹脂組成物。
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~11のいずれか1項に記載の硬化性樹脂組成物。
- 請求項1~12のいずれか1項に記載の硬化性樹脂組成物を硬化してなる硬化膜。
- 請求項13に記載の硬化膜を2層以上含み、前記硬化膜同士のいずれかの間に金属層を含む積層体。
- 請求項1~12のいずれか1項に記載の硬化性樹脂組成物を基材に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
- 前記膜を露光する露光工程及び前記膜を現像する現像工程を含む、請求項15に記載の硬化膜の製造方法。
- 前記膜を50~450℃で加熱する加熱工程を含む、請求項15又は16に記載の硬化膜の製造方法。
- 請求項13に記載の硬化膜又は請求項14に記載の積層体を含む、半導体デバイス。
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WO2022210226A1 (ja) * | 2021-03-31 | 2022-10-06 | 富士フイルム株式会社 | 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、並びに、化合物 |
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WO2023190061A1 (ja) * | 2022-03-29 | 2023-10-05 | 富士フイルム株式会社 | 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
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