WO2015190210A1 - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents
Curable resin composition, dry film, cured product, and printed wiring board Download PDFInfo
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- WO2015190210A1 WO2015190210A1 PCT/JP2015/063870 JP2015063870W WO2015190210A1 WO 2015190210 A1 WO2015190210 A1 WO 2015190210A1 JP 2015063870 W JP2015063870 W JP 2015063870W WO 2015190210 A1 WO2015190210 A1 WO 2015190210A1
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- resin
- resin composition
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- curable resin
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- 0 C1CC=*CC1 Chemical compound C1CC=*CC1 0.000 description 2
- MZSMMXPTQDOEJI-UHFFFAOYSA-N CNC(Cc(cc1)cc(C(N2C)=O)c1C2=O)=O Chemical compound CNC(Cc(cc1)cc(C(N2C)=O)c1C2=O)=O MZSMMXPTQDOEJI-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
-
- 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
-
- 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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- the present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board, and more specifically, a curable resin capable of obtaining a cured product having better resolution, toughness, and heat resistance than before.
- the present invention relates to a composition, a dry film, a cured product, and a printed wiring board.
- solder resist compositions for some consumer printed wiring boards and most industrial printed wiring boards are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density.
- a liquid development type solder resist composition that is finish-cured (mainly cured) by at least one of irradiation is used.
- alkali development type photo solder resist compositions using an aqueous alkali solution as a developing solution have become mainstream, and are used in large quantities in the production of actual printed wiring boards.
- Patent Document 1 proposes a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. Has been.
- phenol novolac type (cresol novolac type) epoxy acrylate resin and acrylic copolymer type resin are widely used in the alkali-soluble type.
- phenol novolac epoxy acrylate resins are not necessarily excellent in toughness, and acrylic copolymer resins are inferior in heat resistance.
- semiconductor package components are mounted on a printed wiring board, the number of connected IOs and the size of the components are simultaneously reduced, and the wiring density is rapidly increased. In order to enable high-density wiring, a curable resin composition having high resolution is required.
- an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board that can obtain a cured product that is superior in resolution, toughness, and heat resistance than before. There is.
- the present inventors have made the resin used in the curable resin composition a resin having a specific structure, and set the particle size of the inorganic particles as the filler to a predetermined value. By making it below the value, it was found that the above problems could be solved, and the present invention was completed.
- the curable resin composition of the present invention comprises (A) the following formulas (1), (2), An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a compound having the following.
- the curable resin composition of the present invention may contain a resin having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group.
- the inorganic particles (B) having an average particle diameter of 200 nm or less are preferably silica.
- (E) thermosetting resin is included.
- the (E) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.
- the dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention on a film.
- the cured product of the present invention is characterized in that the curable resin composition of the present invention is cured, or the resin layer of the dry film of the present invention is cured.
- the printed wiring board of the present invention is characterized by comprising the cured product of the present invention.
- a curable resin composition a dry film, a cured product, and a printed wiring board capable of obtaining a cured product having excellent resolution, toughness, and heat resistance.
- the curable resin composition of the present invention (hereinafter also referred to as “resin composition”) is (A) the following formulas (1), (2), An amide-imide resin (hereinafter also referred to as “component (A)”) having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “component”), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), (D) a compound having an unsaturated double bond (hereinafter referred to as “component (D)”) Included).
- component (A) An amide-imide resin having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “com
- the resin composition of the present invention can be developed with a weak alkaline aqueous solution such as a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, or an ammonia aqueous solution, and it is not necessary to use a strong alkaline developer during development. Further, since development is possible with a weak alkaline aqueous solution, the environmental load is small.
- the resin composition of the present invention has a solubility in an aqueous sodium carbonate solution (30 ° C., 1 mass%) of 0.05 g / L or more per minute.
- the component (A) of the resin composition of the present invention has the following formula (1) or (2), It is an amide imide resin which has at least one structure represented by these, and an alkali-soluble functional group.
- the resin composition of the present invention contains a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained.
- the amidoimide resin having the structure represented by (1) is excellent in light transmittance, the resolution of the resin composition can be improved.
- the component (A) preferably has transparency.
- the transmittance of light having a wavelength of 365 nm is 70% or more in the dry coating film 25 ⁇ m of the component (A). Is preferred.
- the content of the structures of the formulas (1) and (2) in the component (A) of the resin composition of the present invention is preferably 10 to 70% by mass.
- a cured product having excellent solvent solubility and excellent physical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained.
- the amount is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
- amideimide resin having the structure represented by the formula (1) in particular, the formula (3A) or (3B) (In the formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group.
- a resin having a structure represented by a bond, an alkylene group such as CH 2 or C (CH 3 ) 2 ) is preferable because it has excellent physical properties such as tensile strength and elongation and dimensional stability.
- a resin having 10 to 100% by mass of the structure of the formulas (3A) and (3B) can be preferably used. More preferably, it is 20 to 80% by mass.
- an amidoimide resin containing 5 to 100 mol% of the structure of the formulas (3A) and (3B) is preferably used from the viewpoint of solubility and mechanical properties. Can do.
- the amount is more preferably 5 to 98 mol%, further preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.
- amide imide resin which has a structure represented by Formula (2), especially Formula (4A) or (4B) (In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group, It is preferable that the resin having a structure represented by a bond or an alkylene group such as CH 2 or C (CH 3 ) 2 is a cured product having excellent mechanical properties such as tensile strength and elongation. To preferred.
- a resin having a structure of formulas (4A) and (4B) of 10 to 100% by mass can be preferably used. More preferably, it is 20 to 80% by mass.
- an amideimide resin containing 2 to 95 mol% of the structures of the formulas (4A) and (4B) can also be preferably used because it exhibits good mechanical properties. More preferably, it is 10 to 80 mol%.
- a component can be obtained by a well-known method.
- the amidoimide resin having the structure (1) can be obtained using, for example, a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic acid anhydride.
- diisocyanate compound having a biphenyl skeleton examples include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl and 4,4′-diisocyanate-3,3′-diethyl-1,1′-biphenyl.
- 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate- Examples include 3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl, and the like.
- aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.
- cyclohexane polycarboxylic acid anhydride examples include cyclohexane tricarboxylic acid anhydride and cyclohexane tetracarboxylic acid anhydride.
- the amidoimide resin having the structure (2) can be obtained by using, for example, the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid hydrate having two acid anhydride groups.
- polycarboxylic acid anhydrides having two acid anhydride groups examples include pyromellitic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl- 2,2 ′, 3,3′-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis
- the component (A) of the resin composition of the present invention has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By having an alkali-soluble functional group, it becomes a resin composition capable of alkali development.
- the alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, etc., and preferably contains a carboxyl group.
- the acid value of the component (A) in the resin composition of the present invention is preferably in the range of 20 to 120 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. By making the acid value of the component (A) within the above range, alkali development can be performed satisfactorily, and a normal cured product pattern can be formed.
- the weight average molecular weight of the component (A) of the resin composition of the present invention varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the moisture resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, developability and storage stability are good. More preferably, it is 5,000 to 100,000.
- component (A) examples include Unidic V-8000 series from DIC Corporation and SOXR-U from Nippon Kogyo Paper Industries.
- the resin composition of the present invention may contain a resin having a different structure from the component (A) and having an alkali-soluble functional group (hereinafter also referred to as the component (A1)).
- a resin having a different structure from the component (A) and having an alkali-soluble functional group hereinafter also referred to as the component (A1).
- the difference between the component (A) and the structure means that it does not include the structures of the formulas (1) and (2).
- the alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A).
- a carboxyl group-containing resin starting from an epoxy resin a carboxyl group-containing resin having a urethane skeleton (also referred to as a carboxyl group-containing urethane resin), and a carboxyl group having a copolymer structure of an unsaturated carboxylic acid -Containing resins, carboxyl group-containing resins starting from phenolic compounds, and carboxyl group-containing resins obtained by adding compounds having one epoxy group and one or more (meth) acryloyl groups in the molecule to these carboxyl group-containing resins It is preferably at least one of resins. Specific examples of the component (A1) are shown below.
- a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
- carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
- one isocyanate group and one or more (meth) acryloyl groups in the molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate
- a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
- (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl groups present in the side chain are added to 2 such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
- the epoxy resin is preferably solid.
- (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the resulting hydroxyl group.
- Carboxyl group-containing photosensitive resin is preferably solid.
- a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polyvalent.
- a carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
- one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate.
- a carboxyl group-containing photosensitive resin obtained by adding a compound having the same.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions hereinafter.
- the acid value and weight average molecular weight of the component (A1) are in the same range as the acid value and weight average molecular weight of the component (A).
- the blending amount of the component (A1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass with respect to 100 parts by mass in total of the component (A) and the component (A1). It is as follows. By setting it as said range, the hardened
- the resin composition of the present invention includes (B) inorganic particles having an average particle size of 200 nm or less.
- the average particle diameter of the inorganic particles is preferably 150 nm or less, and more preferably 100 nm or less.
- the reason why the average particle size of the inorganic particles is 200 nm or less is as follows. That is, normally, an ultraviolet wavelength having a wavelength of 450 nm or less is used for exposure of the resin composition. In order to improve the resolution of the resin composition, it is necessary to suppress the scattering of light. However, when the inorganic particles in the resin composition are exposed to light, the light is scattered. As the particle size is smaller, the scattering is reduced.
- the resolution is greatly improved by setting the particle size of the inorganic particles to 200 nm or less, which is about half the wavelength of ultraviolet rays for exposure. It was found that it can be improved.
- the average particle diameter is a value measured by a laser diffraction method. Nikkiso Co., Ltd. (Nanotrac wave) etc. are mentioned as a measuring apparatus by a laser diffraction method.
- the surface of the cured product is first etched by plasma treatment so that the inorganic particles can be seen, and the inorganic particles are observed with a scanning electron microscope (SEM). To do. To obtain the average particle size of the inorganic particles, measure the diameter of the observed inorganic particles in the range of 1 ⁇ m 2 , perform the operation five times including other points, and calculate the average value of the inorganic particle diameters. do it.
- a MARCH PLASMA SYSTEM INC AP-1000 is used as an apparatus, and POWER: 500 W, Pressure: 300 Torr, Gas: Ar, and a treatment time of 10 minutes.
- the inorganic particles include known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicin, and silicocolloid. Can be used. Among these, silica having a small linear expansion coefficient can be suitably used. In addition, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type.
- inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicin, and silicocolloid. Can be used. Among these, silica having a small linear expansion coefficient can be suitably used. In addition, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type.
- the blending amount of the component (B) in the resin composition of the present invention is 100 parts by mass in total of the component (A) and the component (A1) (when not including the component (A1), 100 parts by mass of the component (A)).
- the amount is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass.
- the resin composition of this invention is made by making (B) component 150 mass parts or less. It is possible to prevent deterioration in workability during application.
- silica having a small linear expansion coefficient can be suitably used as the component (B).
- the surface of the silica is treated with a silane coupling agent.
- a silane coupling agent are preferred. This is because precipitation and aggregation can be prevented after being dispersed in the liquid, and as a result, the storage stability is excellent.
- Examples of the organic group contained in the silane coupling agent include vinyl, epoxy, styryl, methacryloxy, acryloxy, amino, ureido, chloropropyl, mercapto, polysulfide, and isocyanate groups. Can be mentioned.
- a silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
- the resin composition of the present invention contains (C) a photopolymerization initiator.
- a photopolymerization initiator an oxime ester system including a structure represented by the general formula (I), an ⁇ -aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III)
- the photopolymerization initiator an oxime ester system including a structure represented by the general formula (I), an ⁇ -aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III) It is preferable to contain 1 type (s) or 2 or more types selected from the group which consists of the acylphosphine oxide type
- R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.
- R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.
- the phenyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.
- the alkyl group represented by R 1 and R 2 is preferably an alkyl group having 1 to 20 carbon atoms and may contain one or more oxygen atoms in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups.
- the cycloalkyl group represented by R 1 and R 2 is preferably a cycloalkyl group having 5 to 8 carbon atoms.
- the alkanoyl group represented by R 1 and R 2 is preferably an alkanoyl group having 2 to 20 carbon atoms.
- the benzoyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.
- R 3 and R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group
- R 5 and R 6 each independently represent a hydrogen atom or a carbon number 1 to 6 alkyl groups may be represented, or two may combine to form a cyclic alkyl ether group.
- R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group.
- R 9 and R 10 each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.
- oxime ester photopolymerization initiator examples include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
- examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka.
- a photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be suitably used.
- Specific examples include oxime ester compounds represented by the following general formula (V).
- X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, a carbon number of 1
- An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene Thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)
- X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that
- R 1 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
- R 3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a phenyl group.
- R 4 represents a benzyl group or an acyl group represented by X—C ( ⁇ O) —, wherein X is substituted with an alkyl group having 1 to 4 carbon atoms.
- Aryl group or thienyl group A morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).
- ⁇ -aminoacetophenone photopolymerization initiator examples include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.), 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a commercially available compound or a solution thereof can be used.
- 4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.)
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). ) -2,4,4-trimethyl-pentylphosphine oxide.
- examples of commercially available products include Lucilin TPO and Irgacure 819 manufactured by BASF.
- titanocene photopolymerization initiator bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is used. Can be mentioned. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.
- photopolymerization initiators examples include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2 Thioxanthones such as 1,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketone
- one or more known photosensitizers such as tertiary amines such as triethanolamine can be used in combination.
- a 3-substituted coumarin dye, a leuco dye, or the like can be used in combination as a curing aid, if necessary.
- the blending ratio of the component (C) is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)).
- the amount is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass.
- the resin composition of the present invention contains (D) a compound having an unsaturated double bond.
- the component (D) can be photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the resin composition of the present invention in an alkaline aqueous solution.
- polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaery
- Polyacid acrylates of sidyl ether not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.
- an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
- a hydroxy acrylate such as pentaerythritol triacrylate
- a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
- an epoxy urethane acrylate compound obtained by reacting a half urethane compound.
- Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
- a compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more.
- the blending ratio of the component (D) is preferably 1 to 60 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)).
- the amount is more preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass.
- the resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter also referred to as “component (E)”).
- thermosetting resins include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. in one molecule such as two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, block isocyanate compounds, etc.
- thermosetting resins such as bismaleimide, oxazine, cyclocarbonate compounds and carbodiimide resins Can be mentioned.
- the epoxy resin a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used.
- the epoxy resin may be liquid or may be solid or semi-solid.
- Polyfunctional epoxy resins include: bisphenol A type epoxy resins; brominated epoxy resins; novolac type epoxy resins; bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resins; glycidyl amine type epoxy resins; Epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; Resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl meta Acrylate copolymer based epoxy resins; polybuta
- the epoxy resin is preferably a bisphenol A type or bisphenol F type novolak type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolak type (biphenylaralkyl type) epoxy resin, a naphthalene type epoxy resin or a mixture thereof. .
- thermosetting resin an epoxy resin having a naphthalene skeleton is preferable as the thermosetting resin.
- naphthalene has a planar structure, can reduce the coefficient of linear expansion, and can further improve heat resistance.
- thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available epoxy resins having a naphthalene skeleton include ESN-190 and ESN-360 manufactured by Nippon Steel Chemical, EPICRON HP-4032 and EPICRON HP-4032D manufactured by DIC.
- thermosetting resin having an alicyclic skeleton is preferable, for example, a dicyclopentadiene skeleton-containing thermosetting resin is preferable, and a dicyclopentadiene skeleton-containing epoxy resin is particularly preferable. Further, a thermosetting resin having an alicyclic skeleton is preferable because an effect of improving the glass transition temperature is obtained as compared with an epoxy resin having a chain skeleton.
- the blending ratio of the component (E) is preferably 10 to 100 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). More preferably, it is 10 to 80 parts by mass. (E) By making the compounding quantity of a component into the said range, the composition which has heat resistance and has both favorable developability and photoreactivity can be obtained.
- thermosetting catalyst When the resin composition of the present invention contains (E) a thermosetting resin, a thermosetting catalyst may be included.
- the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide, and phosphorus compounds such
- thermosetting catalysts examples include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the blending amount of the thermosetting catalyst is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). On the other hand, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass.
- the resin composition of the present invention can use an organic solvent for the preparation of the composition or for adjusting the viscosity for application to a substrate or a carrier film.
- organic solvent examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
- ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Esters such as propylene glycol butyl ether acetate; ethanol, propanol Ethylene glycol, or propylene glycol; octane, alipha
- the resin composition of the present invention comprises (A) an amide-imide resin having at least one structure represented by the above formula (1) or (2) and an alkali-soluble functional group, and (B) an inorganic having an average particle size of 200 nm or less. It is characterized by containing particles, (C) a photoinitiator, and (D) a compound having an unsaturated double bond, and there is no particular limitation for the rest.
- a known and commonly used colorant for example, a white colorant such as titanium oxide, a black colorant such as carbon black or titanium black, phthalocyanine blue, phthalocyanine green, or disazo yellow is used as necessary. Etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like can be added.
- the resin composition of the present invention is suitable for forming an insulating cured film on a printed wiring board, more preferably for forming an insulating permanent film, and for forming a coverlay, solder resist, and interlayer insulating material. Is optimal.
- the resin composition of this invention can also be used for formation of a solder dam etc.
- the resin composition of the present invention may be a liquid type or a dry film type obtained by drying a liquid type resin composition.
- the liquid resin composition may be a two-component type from the viewpoint of storage stability, but may be a one-component type.
- the dry film of the present invention has a resin layer obtained by applying the resin composition of the present invention on a film (hereinafter also referred to as “carrier film”) and then drying it.
- the dry film of the present invention is prepared by diluting the resin composition of the present invention with an organic solvent so as to have an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It can be obtained by applying a uniform thickness on a carrier film with a coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying may be appropriately set in the range of 5 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
- the film is not limited to a carrier film but may be a cover film.
- a plastic film can be suitably used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
- a peelable cover film may be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film.
- a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
- Volatile drying performed after the resin composition of the present invention is applied on a carrier film is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with an air heating heat source using steam). And a method of spraying the hot air against the support from a nozzle).
- the cured product of the present invention is a product obtained by curing the resin composition of the present invention and a product obtained by curing the resin layer of the dry film of the present invention.
- the cured product of the present invention is obtained by applying an active energy ray to the coating film obtained after applying the resin composition of the present invention and evaporating and drying the solvent, or by irradiating the active film with an active energy ray. It can be obtained by curing an exposed portion which is a portion irradiated with active energy rays.
- the printed wiring board of the present invention comprises the cured product of the present invention.
- the printed wiring board of this invention can be obtained by the method of apply
- the resin composition of the present invention is directly coated on the printed wiring board on which a circuit is formed, and after forming a coating film of the resin composition, laser light, etc. Directly irradiate the active energy rays according to the pattern or selectively irradiate the active energy rays through the photomask on which the pattern is formed, and develop the unexposed area with a dilute alkaline aqueous solution to form a resist pattern. To do.
- the printed wiring board having the cured product pattern is manufactured by irradiating the resist pattern with active energy rays at, for example, 500 to 2000 mJ / cm 2 and curing it by heating to a temperature of about 140 to 180 ° C., for example. Irradiation of the active energy ray to the resist pattern is performed in order to almost completely cure the component (D) that did not react by exposure when forming an image of the resist pattern.
- the carrier film is peeled off and developed in the same manner as described above. Thereafter, the resin layer is irradiated with active energy rays and heated to a temperature of about 140 to 180 ° C. for curing to produce a printed wiring board having a cured product pattern.
- the cured film pattern may be formed by a photolithography method or a screen printing method.
- a direct drawing apparatus such as a direct imaging apparatus that directly draws an image with active energy rays by CAD data from a computer can be used.
- a light source for the direct drawing apparatus either a mercury short arc lamp, an LED, or a laser beam having a maximum wavelength in the range of 350 to 410 nm may be used.
- the exposure amount for forming the image of the resist pattern varies depending on the film thickness and the like, but can be generally in the range of 20 to 1500 mJ / cm 2 , preferably 20 to 1200 mJ / cm 2 .
- a developing method As a developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be adopted, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate An aqueous alkali solution such as ammonia or amines can be used.
- Examples 1 to 25 and Comparative Examples 1 to 3 Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below.
- the obtained resin composition was applied on the entire surface of a patterned copper foil substrate for evaluation by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, the obtained evaluation substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Developed for seconds. After forming the resist pattern of the cured product, it was cured by UV irradiation at 180 ° C.
- the amide imide resin (A-1), other resins (A1-1), and (A1-2) were synthesized according to the following synthesis method.
- the obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, linear expansion coefficient, and glass transition point.
- the average particle size of the inorganic particles in Tables 1 to 4 is a value measured by a laser diffraction method.
- the optimal exposure amount was calculated
- Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. Next, the copper-clad laminated substrate was polished with buffalo, washed with water and dried, and the obtained resin composition was applied by a screen printing method and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2).
- the irradiated piece was used as a test piece, and after developing for 60 seconds with a developer having a spray pressure of 2 kg / cm 2 (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 10 was determined as the appropriate exposure amount.
- polyamideimide resin (A1) having a resin solid content of 17% with a viscosity of 7 Pa ⁇ s at 25 ° C. and a solution acid value of 5.3 (KOHmg / g) (resin composition in which the resin is dissolved in ⁇ -butyrolactone) Got.
- the solid content acid value of the resin was 31.2 (KOH mg / g).
- the polyamideimide resin (A-1) is a resin having a structure of the above formulas (1) and (2) and a carboxyl group.
- reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
- the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
- a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
- A Stress at break 80 N / mm 2 or more / elongation 3% or more
- B Stress at break 50 N / mm 2 or more, less than 80 N / mm 2 / elongation 2% or more and less than 3%
- C Stress at break 50 less than N / mm 2 / elongation Less than 2%
- Tg 180 ° C. or more / CTE less than 40 ppm
- B Tg 150 ° C. or more, less than 180 ° C./CTE less than 50 ppm, 40 ppm or more
- C Tg less than 150 ° C./CTE 50 ppm or more
- developability that is, (change in weight of substrate: g) / (volume of developer: L) was calculated and evaluated. It can be seen that the higher the developability value, the faster the development speed.
- a composition containing a general polyimide resin (TECHMIGHT E2020, manufactured by Air Water Co., Ltd.)
- the developability is 0.01 g / L or less, which is almost insoluble.
- Amidoimide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kogyo Paper Industries Co., Ltd.), corresponding to other carboxyl group-containing amidoimide resins having the structure of the above formula (2) (A1 -1): carboxyl group-containing resin synthesized in Synthesis Example 2 (solid content 65%)
- the resin composition of the present invention can obtain a cured product having excellent resolution, heat resistance, and toughness. Moreover, it turns out that the dry film obtained from the resin composition of this invention is excellent in workability
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Abstract
Description
で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂と、(B)平均粒径が200nm以下の無機粒子と、(C)光重合開始剤と、(D)不飽和二重結合を有する化合物と、を含むことを特徴とするものである。 That is, the curable resin composition of the present invention comprises (A) the following formulas (1), (2),
An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a compound having the following.
本発明の硬化性樹脂組成物(以下、「樹脂組成物」とも称す。)は、(A)下記式(1)、(2)、
で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂(以下、「(A)成分」とも称す)と、(B)平均粒径が200nm以下の無機粒子(以下、「(B)成分」とも称す)と、(C)光重合開始剤(以下、「(C)成分」とも称す)と、(D)不飽和二重結合を有する化合物と(以下、「(D)成分」とも称す)、を含む。樹脂組成物の樹脂成分として上記構造を有する樹脂を用い、かつ、充填剤として平均粒径が200nm以下の無機粒子を用いることで、解像性、強靭性、耐熱性に優れた硬化物を得ることができる。 [Curable resin composition]
The curable resin composition of the present invention (hereinafter also referred to as “resin composition”) is (A) the following formulas (1), (2),
An amide-imide resin (hereinafter also referred to as “component (A)”) having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “component”), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), (D) a compound having an unsaturated double bond (hereinafter referred to as “component (D)”) Included). By using a resin having the above structure as the resin component of the resin composition and using inorganic particles having an average particle size of 200 nm or less as a filler, a cured product having excellent resolution, toughness, and heat resistance is obtained. be able to.
<(A)成分>
本発明の樹脂組成物の(A)成分は、下記式(1)または(2)、
で表される少なくとも一方の構造と、アルカリ可溶性官能基と、を有するアミドイミド樹脂である。本発明の樹脂組成物が、シクロヘキサン環またはベンゼン環に直結したイミド結合を有する樹脂を含むことにより、強靭性および耐熱性に優れた硬化物を得ることができる。特に、(1)で表される構造を有するアミドイミド樹脂は、光の透過性に優れるため、樹脂組成物の解像性を向上させることができる。本発明の樹脂組成物においては、(A)成分は、透明性を有することが好ましく、例えば、(A)成分の乾燥塗膜25μmにおいて、波長365nmの光の透過率は70%以上であることが好ましい。 Hereinafter, each component of the resin composition of this invention is demonstrated in detail.
<(A) component>
The component (A) of the resin composition of the present invention has the following formula (1) or (2),
It is an amide imide resin which has at least one structure represented by these, and an alkali-soluble functional group. When the resin composition of the present invention contains a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained. In particular, since the amidoimide resin having the structure represented by (1) is excellent in light transmittance, the resolution of the resin composition can be improved. In the resin composition of the present invention, the component (A) preferably has transparency. For example, the transmittance of light having a wavelength of 365 nm is 70% or more in the dry coating film 25 μm of the component (A). Is preferred.
(式(3A)および(3B)中、それぞれ、Rは1価の有機基であり、H、CF3またはCH3であることが好ましく、Xは直接結合または2価の有機基であり、直接結合、CH2またはC(CH3)2等のアルキレン基であることが好ましい。)で表される構造を有する樹脂が、引張強度や伸度等の物性および寸法安定性に優れるため好ましい。本発明の樹脂組成物においては、溶解性や機械物性の観点から、(A)成分として、式(3A)および(3B)の構造を10~100質量%有する樹脂を好適に用いることができる。より好ましくは20~80質量%である。 As the amideimide resin having the structure represented by the formula (1), in particular, the formula (3A) or (3B)
(In the formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group. A resin having a structure represented by a bond, an alkylene group such as CH 2 or C (CH 3 ) 2 ) is preferable because it has excellent physical properties such as tensile strength and elongation and dimensional stability. In the resin composition of the present invention, from the viewpoint of solubility and mechanical properties, as the component (A), a resin having 10 to 100% by mass of the structure of the formulas (3A) and (3B) can be preferably used. More preferably, it is 20 to 80% by mass.
(式(4A)および(4B)中、それぞれ、Rは1価の有機基であり、H、CF3またはCH3であることが好ましく、Xは直接結合または2価の有機基であり、直接結合、CH2またはC(CH3)2などのアルキレン基であることが好ましい。)で表される構造を有する樹脂が、引張強度や伸度等の機械的物性に優れる硬化物が得られることから好ましい。本発明の樹脂組成物においては、溶解性や機械物性の観点から、(A)成分として、式(4A)および(4B)の構造を10~100質量%有する樹脂を好適に用いることができる。より好ましくは20~80質量%である。 Moreover, as an amide imide resin which has a structure represented by Formula (2), especially Formula (4A) or (4B)
(In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group, It is preferable that the resin having a structure represented by a bond or an alkylene group such as CH 2 or C (CH 3 ) 2 is a cured product having excellent mechanical properties such as tensile strength and elongation. To preferred. In the resin composition of the present invention, from the viewpoints of solubility and mechanical properties, as the component (A), a resin having a structure of formulas (4A) and (4B) of 10 to 100% by mass can be preferably used. More preferably, it is 20 to 80% by mass.
(2)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネートなどのジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸などのカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物などのジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。
(3)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネートなどのジイソシアネート化合物と、ポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物などのジオール化合物の重付加反応によるウレタン樹脂の末端に酸無水物を反応させてなる末端カルボキシル基含有ウレタン樹脂。
(4)ジイソシアネートと、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂などの2官能エポキシ樹脂の(メタ)アクリレートもしくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有感光性ウレタン樹脂。
(5)上述した(2)または(4)の樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレートなどの分子中に1つの水酸基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有感光性ウレタン樹脂。
(6)上述した(2)または(4)の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子中に1つのイソシアネート基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有感光性ウレタン樹脂。
(7)後述するような2官能またはそれ以上の多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸などの2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。ここで、エポキシ樹脂は、固形であることが好ましい。
(8)後述するような2官能エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。ここで、エポキシ樹脂は、固形であることが好ましい。
(9)ノボラックなどの多官能フェノール化合物にエチレンオキサイドなどの環状エーテル、または、プロピレンカーボネートなどの環状カーボネートを付加させ、得られた水酸基を(メタ)アクリル酸で部分エステル化し、残りの水酸基に多塩基酸無水物を反応させたカルボキシル基含有感光性樹脂。
(10)これら(1)~(9)の樹脂に、さらにグリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレートなどの分子中に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。 (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(5) During the synthesis of the resin described in (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing photosensitive urethane resin.
(6) During the synthesis of the resin of (2) or (4) described above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
(7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl groups present in the side chain are added to 2 such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which a basic acid anhydride is added. Here, the epoxy resin is preferably solid.
(8) (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin. Here, the epoxy resin is preferably solid.
(9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polyvalent. A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
(10) In addition to these resins (1) to (9), one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound having the same.
本発明の樹脂組成物は、(B)平均粒径が200nm以下の無機粒子を含む。(B)無機粒子の平均粒径は、好適には150nm以下であり、より好適には100nm以下である。無機粒子の平均粒径を200nm以下とする理由は以下のとおりである。すなわち、通常、樹脂組成物の露光には、波長が450nm以下の紫外線波長が用いられる。樹脂組成物の解像性を良好にするためには光の散乱を抑えることが必要であるが、樹脂組成物中の無機粒子に光があたると、光は散乱を起こす。粒子径が小さいほど散乱は少なくなるが、本発明者らの検討の結果、無機粒子の粒径を、露光用の紫外線の波長の半分程度である200nm以下とすることにより、解像性を大幅に向上できることが分かった。ここで平均粒径は、レーザー回折法により測定された値である。レーザー回折法による測定装置としては、日機装株式会社(Nanotrac wave)などが挙げられる。 <(B) component>
The resin composition of the present invention includes (B) inorganic particles having an average particle size of 200 nm or less. (B) The average particle diameter of the inorganic particles is preferably 150 nm or less, and more preferably 100 nm or less. The reason why the average particle size of the inorganic particles is 200 nm or less is as follows. That is, normally, an ultraviolet wavelength having a wavelength of 450 nm or less is used for exposure of the resin composition. In order to improve the resolution of the resin composition, it is necessary to suppress the scattering of light. However, when the inorganic particles in the resin composition are exposed to light, the light is scattered. As the particle size is smaller, the scattering is reduced. However, as a result of the study by the present inventors, the resolution is greatly improved by setting the particle size of the inorganic particles to 200 nm or less, which is about half the wavelength of ultraviolet rays for exposure. It was found that it can be improved. Here, the average particle diameter is a value measured by a laser diffraction method. Nikkiso Co., Ltd. (Nanotrac wave) etc. are mentioned as a measuring apparatus by a laser diffraction method.
本発明の樹脂組成物は、(C)光重合開始剤を含む。(C)光重合開始剤としては、一般式(I)で表される構造を含むオキシムエステル系、一般式(II)で表される構造を含むα-アミノアセトフェノン系、一般式(III)で表される構造を含むアシルホスフィンオキサイド系、および一般式(IV)で表される構造のチタノセン系からなる群から選択される1種または2種以上を含有することが好ましい。 <(C) component>
The resin composition of the present invention contains (C) a photopolymerization initiator. (C) As the photopolymerization initiator, an oxime ester system including a structure represented by the general formula (I), an α-aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III) It is preferable to contain 1 type (s) or 2 or more types selected from the group which consists of the acylphosphine oxide type | system | group containing the structure represented, and the titanocene type | system | group of the structure represented by general formula (IV).
(一般式(V)中、Xは、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)を表し、Y、Zはそれぞれ、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、ハロゲン基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Arは、結合か、炭素数1~10のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、2,5-ピロール-ジイル、4,4’-スチルベン-ジイル、4,2’-スチレン-ジイルで表し、nは0か1の整数である。) Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be suitably used. Specific examples include oxime ester compounds represented by the following general formula (V).
(In the general formula (V), X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, a carbon number of 1 Substituted with an alkoxy group having 8 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms) Substituted with an alkoxy group, an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are a hydrogen atom and an alkyl group having 1 to 17 carbon atoms, respectively. An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms). Alkylamino group substituted by alkylamino group or dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene Thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)
(一般式(VI)中、R1は、炭素原子数1~4のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数1~4のアルキル基で置換されていてもよいフェニル基を表す。R2は、炭素原子数1~4のアルキル基、炭素原子数1~4のアルコキシ基、または、炭素原子数1~4のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。R3は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数1~20のアルキル基、炭素原子数1~4のアルコキシ基で置換されていてもよいベンジル基を表す。R4は、ニトロ基、または、X-C(=O)-で表されるアシル基を表す。Xは、炭素原子数1~4のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式(VII)で示される構造を表す。)
Moreover, the compound which can be represented by the following general formula (VI) as a preferable carbazole oxime ester compound can also be mentioned.
(In the general formula (VI), R 1 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group. R 3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a phenyl group. R 4 represents a benzyl group or an acyl group represented by X—C (═O) —, wherein X is substituted with an alkyl group having 1 to 4 carbon atoms. Aryl group or thienyl group , A morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).
本発明の樹脂組成物は、(D)不飽和二重結合を有する化合物を含有する。(D)成分は、活性エネルギー線の照射により光硬化して、本発明の樹脂組成物をアルカリ水溶液に不溶化し、または不溶化を助けることができる。このような化合物としては、慣用公知のポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ウレタン(メタ)アクリレート、カーボネート(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレートが使用でき、具体的には、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類;エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類;N,N-ジメチルアクリルアミド、N-メチロールアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類;N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類;ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス-ヒドロキシエチルイソシアヌレートなどの多価アルコールまたはこれらのエチレオキサイド付加体、プロピレンオキサイド付加体、もしくはε-カプロラクトン付加体などの多価アクリレート類;フェノキシアクリレート、ビスフェノールAジアクリレート、およびこれらのフェノール類のエチレンオキサイド付加体もしくはプロピレンオキサイド付加体などの多価アクリレート類;グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類;上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および上記アクリレートに対応する各メタクリレート類の少なくとも何れか1種などを挙げることができる。 <(D) component>
The resin composition of the present invention contains (D) a compound having an unsaturated double bond. The component (D) can be photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the resin composition of the present invention in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyvalent acrylates such as ε-caprolactone adduct; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.
本発明の樹脂組成物は、さらに耐熱性を向上させるために、(E)熱硬化性樹脂(以下、「(E)成分」とも称す)を含有させることが好ましい。熱硬化性樹脂としては、例えば、多官能エポキシ化合物、多官能オキセタン化合物、エピスルフィド樹脂等分子中に2個以上の環状エーテル基および/または環状チオエーテル基、ポリイソシアネート化合物、ブロックイソシアネート化合物等1分子内に2個以上のイソシアネート基、またはブロック化イソシアネート基を有する化合物、メラミン樹脂、ベンゾグアナミン樹脂等のアミン樹脂とその誘導体、ビスマレイミド、オキサジン、シクロカーボネート化合物、カルボジイミド樹脂等の公知の熱硬化性樹脂が挙げられる。 <(E) Thermosetting resin>
In order to further improve the heat resistance, the resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter also referred to as “component (E)”). Examples of thermosetting resins include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. in one molecule such as two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, block isocyanate compounds, etc. Compounds having two or more isocyanate groups or blocked isocyanate groups, amine resins such as melamine resins and benzoguanamine resins and derivatives thereof, known thermosetting resins such as bismaleimide, oxazine, cyclocarbonate compounds and carbodiimide resins Can be mentioned.
本発明の樹脂組成物は、(A)上記式(1)または(2)で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂と、(B)平均粒径が200nm以下の無機粒子と、(C)光反応開始剤と、(D)不飽和二重結合を有する化合物と、を含むことが特徴であり、それ以外については特に制限はない。例えば、本発明の樹脂組成物においては、必要に応じて公知慣用の着色剤(例えば、酸化チタンなどの白色着色剤、カーボンブラック、チタンブラックなどの黒色着色剤、フタロシアニンブルー、フタロシアニングリーン、ジスアゾイエロー等)、熱重合禁止剤、増粘剤、消泡剤、レベリング剤等を添加することができる。 <Others>
The resin composition of the present invention comprises (A) an amide-imide resin having at least one structure represented by the above formula (1) or (2) and an alkali-soluble functional group, and (B) an inorganic having an average particle size of 200 nm or less. It is characterized by containing particles, (C) a photoinitiator, and (D) a compound having an unsaturated double bond, and there is no particular limitation for the rest. For example, in the resin composition of the present invention, a known and commonly used colorant (for example, a white colorant such as titanium oxide, a black colorant such as carbon black or titanium black, phthalocyanine blue, phthalocyanine green, or disazo yellow is used as necessary. Etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like can be added.
本発明のドライフィルムは、本発明の樹脂組成物を、フィルム(以下、「キャリアフィルム」とも称す)上に塗布し、その後乾燥して得られた樹脂層を有するものである。本発明のドライフィルムは、本発明の樹脂組成物を有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~130℃の温度で1~30分間乾燥して得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で5~150μm、好ましくは10~60μmの範囲で適宜設定すればよい。フィルムとしては、キャリアフィルムに限らず、カバーフィルムでもよい。 [Dry film]
The dry film of the present invention has a resin layer obtained by applying the resin composition of the present invention on a film (hereinafter also referred to as “carrier film”) and then drying it. The dry film of the present invention is prepared by diluting the resin composition of the present invention with an organic solvent so as to have an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It can be obtained by applying a uniform thickness on a carrier film with a coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but in general, the film thickness after drying may be appropriately set in the range of 5 to 150 μm, preferably 10 to 60 μm. The film is not limited to a carrier film but may be a cover film.
本発明の硬化物は、本発明の樹脂組成物が硬化されてなるもの、および、本発明のドライフィルムの樹脂層が硬化されてなるものである。本発明の硬化物は、本発明の樹脂組成物を塗布し、溶剤を揮発乾燥させた後に得られた塗膜に、またはドライフィルムに対し、活性エネルギー線を照射して露光を行うことにより、活性エネルギー線により照射された部分である露光部を硬化させて得ることができる。 [Cured product]
The cured product of the present invention is a product obtained by curing the resin composition of the present invention and a product obtained by curing the resin layer of the dry film of the present invention. The cured product of the present invention is obtained by applying an active energy ray to the coating film obtained after applying the resin composition of the present invention and evaporating and drying the solvent, or by irradiating the active film with an active energy ray. It can be obtained by curing an exposed portion which is a portion irradiated with active energy rays.
本発明のプリント配線板は、本発明の硬化物を備えるものである。本発明のプリント配線板は、本発明の硬化性樹脂組成物をプリント配線板上に直接塗布する方法と、本発明のドライフィルムを用いる方法とにより得ることができる。 [Printed wiring board]
The printed wiring board of the present invention comprises the cured product of the present invention. The printed wiring board of this invention can be obtained by the method of apply | coating the curable resin composition of this invention directly on a printed wiring board, and the method of using the dry film of this invention.
下記表1~4の配合に従って、実施例1~25および比較例1~3の樹脂組成物を調製した。得られた樹脂組成物をパターン形成された評価用の銅箔基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷した。その後、得られた評価基板に対して、高圧水銀灯を搭載した露光装置を用いて最適露光量でレジストパターンを露光し、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像した。硬化物のレジストパターン形成後には、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分加熱して硬化した。なお、アミドイミド樹脂(A-1)、他の樹脂(A1-1)、(A1-2)については、下記の合成方法に従って合成したものを用いた。得られた評価基板につき、解像性、引張強度、伸び、線膨張係数およびガラス転移点について評価した。表1~4中の無機粒子の平均粒径は、レーザー回折法による測定値である。なお、最適露光量は、以下の手順で求めた。 <Examples 1 to 25 and Comparative Examples 1 to 3>
Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. The obtained resin composition was applied on the entire surface of a patterned copper foil substrate for evaluation by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, the obtained evaluation substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Developed for seconds. After forming the resist pattern of the cured product, it was cured by UV irradiation at 180 ° C. for 60 minutes after irradiation with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm 2 . The amide imide resin (A-1), other resins (A1-1), and (A1-2) were synthesized according to the following synthesis method. The obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, linear expansion coefficient, and glass transition point. The average particle size of the inorganic particles in Tables 1 to 4 is a value measured by a laser diffraction method. In addition, the optimal exposure amount was calculated | required in the following procedures.
下記表1~4の配合に従って、実施例1~25および比較例1~3の樹脂組成物を調製した。次に、銅貼り積層基板をバフロール研磨後、水洗、乾燥し、得られた樹脂組成物をスクリーン印刷法により塗布し、80℃の熱風循環式乾燥炉で30分乾燥させた。乾燥後、フォトマスク(イーストマン・コダック社製、ステップタブレットNo.2)を介して、高圧水銀灯露光装置を用いて露光した。照射したものをテストピースとし、スプレー圧2kg/cm2の現像液(30℃の1質量%炭酸ナトリウム水溶液)にて60秒間の現像を行った後、残存塗膜の段数を目視判定した。残存塗膜の段数が10段になる露光量を適正露光量とした。 <Optimum exposure amount>
Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. Next, the copper-clad laminated substrate was polished with buffalo, washed with water and dried, and the obtained resin composition was applied by a screen printing method and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2). The irradiated piece was used as a test piece, and after developing for 60 seconds with a developer having a spray pressure of 2 kg / cm 2 (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 10 was determined as the appropriate exposure amount.
攪拌装置、温度計およびコンデンサーを付けたフラスコに、GBL(ガンマブチロラクトン)848.8gとMDI(ジフェニルメタンジイソシアネート)57.5g(0.23モル)、DMBPDI(4,4’-ジイソシアネート-3,3’-ジメチル-1,1’-ビフェニル)59.4g(0.225モル)とTMA(無水トリメリット酸)67.2g(0.35モル)とTMA-H(シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物)29.7g(0.15モル)を仕込み、攪拌を行いながら発熱に注意して80℃に昇温し、この温度で1時間かけて溶解、反応させ、さらに2時間かけて160℃まで昇温した後、この温度で5時間反応させた。反応は炭酸ガスの発泡とともに進行し、系内は茶色の透明液体となった。25℃での粘度が7Pa・sの樹脂固形分17%で溶液酸価が5.3(KOHmg/g)のポリアミドイミド樹脂(A1)の溶液(樹脂がγ-ブチロラクトンに溶解した樹脂組成物)を得た。なお、樹脂の固形分酸価は31.2(KOHmg/g)であった。また、ゲルパーミエーションクロマトグラフィー(GPC)の測定の結果、重量平均分子量34,000であった。ポリアミドイミド樹脂(A-1)は、上記式(1)と(2)の構造とカルボキシル基を有する樹脂である。 <Synthesis of Amidoimide Resin (A-1) (Synthesis Example 1)>
A flask equipped with a stirrer, a thermometer and a condenser was charged with 888.8 g of GBL (gamma-butyrolactone), 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4′-diisocyanate-3,3 ′). -Dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol), TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1,3,4-tricarboxylic acid) Acid-3,4-anhydride) 29.7 g (0.15 mol) was added, the temperature was raised to 80 ° C. while paying attention to heat generation while stirring, and the mixture was dissolved and reacted at this temperature for 1 hour. After heating up to 160 ° C. over 2 hours, the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. Solution of polyamideimide resin (A1) having a resin solid content of 17% with a viscosity of 7 Pa · s at 25 ° C. and a solution acid value of 5.3 (KOHmg / g) (resin composition in which the resin is dissolved in γ-butyrolactone) Got. The solid content acid value of the resin was 31.2 (KOH mg / g). Moreover, it was the weight average molecular weight 34,000 as a result of the measurement of a gel permeation chromatography (GPC). The polyamideimide resin (A-1) is a resin having a structure of the above formulas (1) and (2) and a carboxyl group.
ジエチレングリコールモノエチルエーテルアセテート600gにオルソクレゾールノボラック型エポキシ樹脂〔DIC社製EPICLON N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6〕1070g(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360g(5.0モル)、およびハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン4.3gを仕込み、110℃に加熱して2時間反応後、120℃に昇温してさらに12時間反応を行った。得られた反応液に芳香族系炭化水素(ソルベッソ150)415g、メチル-5-ノルボルネン-2,3-ジカルボン酸無水物534g(3.0モル)を仕込み、110℃で4時間反応を行い、冷却後、固形分酸価89mgKOH/g、固形分65%のクレゾールノボラック型カルボキシル基含有樹脂溶液を得た。得られた樹脂を他の樹脂(A1-1)とする。 <Synthesis of Other Resin (A1-1) (Synthesis Example 2)>
Orthocresol novolak type epoxy resin [DICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged, and the reaction was performed at 110 ° C. for 4 hours. After cooling, a cresol novolak-type carboxyl group-containing resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. The obtained resin is referred to as other resin (A1-1).
温度計、窒素導入装置兼アルキレンオキシド導入装置および撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和高分子(株)製、商品名「ショーノールCRG951」、OH当量:119.4)119.4g、水酸化カリウム1.19gおよびトルエン119.4gを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド63.8gを徐々に滴下し、125~132℃、0~4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56gを添加混合して水酸化カリウムを中和し、不揮発分62.1%、水酸基価が182.2g/eq.であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基1当量当りアルキレンオキシドが平均1.08モル付加しているものであった。 <Synthesis of Other Resin (A1-2) (Synthesis Example 3)>
A novolac cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
作成した評価基板の硬化被膜のパターンを1,000倍の走査型電子顕微鏡(SEM)にて観察を行い、以下の評価基準で評価した。得られた結果を表1~4に併記する。
AA:ラインアンドスペース10μm以下を形成可能。
A:ラインアンドスペース15μm以下を形成可能。
B:ラインアンドスペース25μm以下を形成可能。
C:ラインアンドスペース25μmを形成不可能。 <Resolution>
The pattern of the cured film of the prepared evaluation board | substrate was observed with the scanning electron microscope (SEM) of 1,000 times, and the following evaluation criteria evaluated. The obtained results are also shown in Tables 1 to 4.
AA: A line and space of 10 μm or less can be formed.
A: Line and space of 15 μm or less can be formed.
B: Line and space of 25 μm or less can be formed.
C: Line and space 25 μm cannot be formed.
実施例1~25および比較例1~3の樹脂組成物を上記と同じ条件で硬化して得た硬化被膜(10mm×40mm)を、島津製作所社製オートグラフAG-Xにて1mm/minの速度で引張試験を行った。得られた結果を表1~4に併記する。破断点応力と伸び率が大きい場合、強靭性に優れる。
A:破断点応力80N/mm2以上/伸び3%以上
B:破断点応力50N/mm2以上80N/mm2未満/伸び2%以上3%未満
C:破断点応力50N/mm2未満/伸び2%未満 <Tensile strength / elongation (toughness)>
Cured coatings (10 mm × 40 mm) obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as described above were applied at 1 mm / min with an autograph AG-X manufactured by Shimadzu Corporation. Tensile tests were performed at speed. The obtained results are also shown in Tables 1 to 4. When the stress at break and elongation are large, the toughness is excellent.
A: Stress at break 80 N / mm 2 or more / elongation 3% or more B: Stress at break 50 N / mm 2 or more, less than 80 N / mm 2 / elongation 2% or more and less than 3% C: Stress at break 50 less than N / mm 2 / elongation Less than 2%
実施例1~25、比較例1~3の樹脂組成物を上記と同じ条件で硬化して得た3mm×10mmのサイズの硬化被膜を、セイコーインスツル社製TMA6100にて10gの荷重を加えながら一定の昇温速度で0℃~260℃の温度範囲で引張り試験を行った。温度に対する硬化被膜の伸び量から線膨張係数(CTE)を算出した。また、変曲点からガラス転移点(Tg)を得た。得られた結果を表1~4に併記する。Tgが高く、CTEが低い場合、耐熱性に優れている。
A:Tg180℃以上/CTE40ppm未満
B:Tg150℃以上180℃未満/CTE50ppm未満40ppm以上
C:Tg150℃未満/CTE50ppm以上 <Linear expansion coefficient and glass transition point (heat resistance)>
A cured film having a size of 3 mm × 10 mm obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as described above while applying a load of 10 g with TMA6100 manufactured by Seiko Instruments Inc. A tensile test was performed in a temperature range of 0 ° C. to 260 ° C. at a constant rate of temperature increase. The linear expansion coefficient (CTE) was calculated from the amount of elongation of the cured film with respect to temperature. Moreover, the glass transition point (Tg) was obtained from the inflection point. The obtained results are also shown in Tables 1 to 4. When Tg is high and CTE is low, the heat resistance is excellent.
A: Tg 180 ° C. or more / CTE less than 40 ppm B: Tg 150 ° C. or more, less than 180 ° C./CTE less than 50 ppm, 40 ppm or more C: Tg less than 150 ° C./CTE 50 ppm or more
実施例1~25および比較例1~3の樹脂組成物を厚さ38μmのポリエチレンテレフタレート(PET)フィルム上にギャップ60μmのアプリケーターを用いて塗布し、80℃で30分乾燥し、室温まで放冷して、樹脂層を有するドライフィルムを作製した。得られたPETフィルム上の樹脂層を10cm四方の大きさに切り、対角線を作るように折り曲げた。折り曲げた際に、樹脂層がPET上で安定したフィルム状で存在するかを確認した。
A:PETと同様に折り曲げられ、PETから剥がれない。
B:PETから剥がれないが、折り曲げた部分が割れる。
C:折り曲げた部分が割れ、PETから剥がれ落ちる。 <Dry film workability>
The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied onto a polyethylene terephthalate (PET) film having a thickness of 38 μm using an applicator with a gap of 60 μm, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thus, a dry film having a resin layer was produced. The resin layer on the obtained PET film was cut into a size of 10 cm square and bent so as to form a diagonal line. When bent, it was confirmed whether the resin layer was present in a stable film form on PET.
A: It is bent in the same manner as PET and does not peel off from PET.
B: Although it does not peel from PET, the bent part is cracked.
C: The bent part is broken and peeled off from the PET.
実施例1~25及び比較例1~3の樹脂組成物を、銅箔基板に塗布し、乾燥後に、塗膜の面積が10cm×10cmで厚さ50μmとなるように、乾燥塗膜を形成した。ビーカーに3Lの1質量%水酸化ナトリウム水溶液を入れ、30℃に加温して現像液を調製した。また、乾燥塗膜を形成した基板の重量を測定した。そして、現像液に基板を浸漬させ、1分間搖動して取り出した。その後、すぐに基板を水洗し、乾燥させてから再度重量を測定した。基板の重量変化から現像性、即ち、(基板の重量変化:g)/(現像液の体積:L)を計算して評価した。現像性の値が高いほど現像速度が速いことがわかる。なお、一般的なポリイミド樹脂(エア・ウォーター株式会社製、TECHMIGHT E2020)を含む組成物の場合、現像性は0.01g/L以下であり、ほぼ不溶である。 <Developability>
The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied to a copper foil substrate, and after drying, a dry coating film was formed so that the area of the coating film was 10 cm × 10 cm and the thickness was 50 μm. . 3 L of a 1% by mass sodium hydroxide aqueous solution was placed in a beaker and heated to 30 ° C. to prepare a developer. Further, the weight of the substrate on which the dry coating film was formed was measured. Then, the substrate was immersed in the developer, and the substrate was shaken for 1 minute and taken out. Thereafter, the substrate was immediately washed with water, dried, and then weighed again. From the change in weight of the substrate, developability, that is, (change in weight of substrate: g) / (volume of developer: L) was calculated and evaluated. It can be seen that the higher the developability value, the faster the development speed. In the case of a composition containing a general polyimide resin (TECHMIGHT E2020, manufactured by Air Water Co., Ltd.), the developability is 0.01 g / L or less, which is almost insoluble.
アミドイミド樹脂(A-2):SOXR-U(樹脂固形分20%)(ニッポン高度紙工業社製)であり、上記式(2)の構造を有するカルボキシル基含有アミドイミド樹脂に相当
他の樹脂(A1-1):合成例2で合成したカルボキシル基含有樹脂(固形分65%)
他の樹脂(A1-2):合成例3で合成したカルボキシル基含有樹脂(固形分71%)
無機粒子1:平均粒径100nmのシリカ
無機粒子2:平均粒径50nmのシリカ
無機粒子3:平均粒径100nmの硫酸バリウム
無機粒子4:平均粒径1μmのシリカ
光重合開始剤1:BASF社製 TPO
光重合開始剤2:BASF社製 IRG-369
光重合開始剤3:BASF社製 IRG-OXE02
不飽和二重結合を有する化合物1:ジペンタエリスリトールヘキサアクリレート
不飽和二重結合を有する化合物2:ジシクロペンタジエンジアクリレート
熱硬化性樹脂1:ナフタレン骨格含有エポキシ樹脂HP4032(150eq)(DIC社製)
熱硬化性樹脂2:ナフトール変性エポキシ樹脂NC7000(230eq)(日本化薬社製)
熱硬化性樹脂3:ビフェニルアラルキル型エポキシ樹脂NC3000(275eq)(日本化薬社製)
熱硬化性樹脂4:ジシクロペンタジエン骨格含有エポキシ樹脂XD-1000(250eq)(日本化薬社製)
熱硬化性樹脂5:ジシクロペンタジエン骨格エポキシ樹脂HP―7200H(280eq)(DIC社製)
熱硬化触媒1:メラミン
熱硬化触媒2:ジシアンジアミド Amidoimide resin (A-1): Resin synthesized in Synthesis Example 1 (resin solid content: 17%)
Amidoimide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kogyo Paper Industries Co., Ltd.), corresponding to other carboxyl group-containing amidoimide resins having the structure of the above formula (2) (A1 -1): carboxyl group-containing resin synthesized in Synthesis Example 2 (solid content 65%)
Other resin (A1-2): carboxyl group-containing resin synthesized in Synthesis Example 3 (solid content: 71%)
Inorganic particles 1: Silica inorganic particles having an average particle size of 100 nm 2: Silica inorganic particles having an average particle size of 50 nm 3: Barium sulfate inorganic particles having an average particle size of 100 nm 4: Silica photopolymerization initiator having an average particle size of 1 μm 1: manufactured by BASF TPO
Photopolymerization initiator 2: IRG-369 manufactured by BASF
Photopolymerization initiator 3: IRG-OXE02 manufactured by BASF
Compound having unsaturated double bond 1: Dipentaerythritol hexaacrylate Compound having unsaturated double bond 2: Dicyclopentadiene diacrylate thermosetting resin 1: Naphthalene skeleton-containing epoxy resin HP4032 (150 eq) (manufactured by DIC)
Thermosetting resin 2: naphthol-modified epoxy resin NC7000 (230 eq) (manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 3: biphenyl aralkyl type epoxy resin NC3000 (275 eq) (manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 4: Epoxy resin XD-1000 (250 eq) containing dicyclopentadiene skeleton (made by Nippon Kayaku Co., Ltd.)
Thermosetting resin 5: dicyclopentadiene skeleton epoxy resin HP-7200H (280 eq) (manufactured by DIC)
Thermosetting catalyst 1: Melamine thermosetting catalyst 2: Dicyandiamide
Claims (10)
- (A)下記式(1)、(2)、
で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂と、(B)平均粒径が200nm以下の無機粒子と、(C)光重合開始剤と、(D)不飽和二重結合を有する化合物と、を含むことを特徴とする硬化性樹脂組成物。 (A) The following formulas (1), (2),
An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a curable resin composition comprising: - 前記(A)アミドイミド樹脂と構造が異なり、アルカリ可溶性官能基を有する樹脂を含む請求項1記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, comprising a resin having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group.
- 前記(B)平均粒径が200nm以下の無機粒子が、シリカである請求項1記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the inorganic particles (B) having an average particle diameter of 200 nm or less are silica.
- (E)熱硬化性樹脂を含む請求項1記載の硬化性樹脂組成物。 (E) The curable resin composition of Claim 1 containing a thermosetting resin.
- 前記(E)熱硬化性樹脂が脂環式骨格を有するエポキシ樹脂である請求項4記載の硬化性樹脂組成物。 The curable resin composition according to claim 4, wherein the (E) thermosetting resin is an epoxy resin having an alicyclic skeleton.
- 請求項1~5のうちいずれか一項記載の硬化性樹脂組成物が、フィルム上に塗布、乾燥されて得られた樹脂層を有することを特徴とするドライフィルム。 A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to any one of claims 1 to 5 on a film.
- 請求項1~5のうちいずれか一項記載の硬化性樹脂組成物が硬化されてなることを特徴とする硬化物。 A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5.
- 請求項6記載のドライフィルムの樹脂層が硬化されてなることを特徴とする硬化物。 A cured product obtained by curing the resin layer of the dry film according to claim 6.
- 請求項7記載の硬化物を備えてなることを特徴とするプリント配線板。 A printed wiring board comprising the cured product according to claim 7.
- 請求項8記載の硬化物を備えてなることを特徴とするプリント配線板。 A printed wiring board comprising the cured product according to claim 8.
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JP2016527701A JP6799462B2 (en) | 2014-06-12 | 2015-05-14 | Curable resin composition, dry film, cured product and printed wiring board |
CN201580030967.7A CN106662813B (en) | 2014-06-12 | 2015-05-14 | Curable resin composition, dry film, cured product, and printed wiring board |
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JPWO2015190210A1 (en) | 2017-04-20 |
TW201609869A (en) | 2016-03-16 |
CN106662813B (en) | 2021-02-26 |
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TWI704169B (en) | 2020-09-11 |
CN106662813A (en) | 2017-05-10 |
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