WO2012173242A1 - 光硬化性熱硬化性樹脂組成物 - Google Patents
光硬化性熱硬化性樹脂組成物 Download PDFInfo
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- WO2012173242A1 WO2012173242A1 PCT/JP2012/065404 JP2012065404W WO2012173242A1 WO 2012173242 A1 WO2012173242 A1 WO 2012173242A1 JP 2012065404 W JP2012065404 W JP 2012065404W WO 2012173242 A1 WO2012173242 A1 WO 2012173242A1
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0166—Polymeric layer used for special processing, e.g. resist for etching insulating material or photoresist used as a mask during plasma etching
Definitions
- the present invention relates to a photocurable thermosetting resin composition, a dry film, a cured product, and a printed wiring board, and more particularly, a photocurable thermosetting suitable for a solder resist of a printed wiring board, particularly a resist for an IC package.
- the present invention relates to a resin composition.
- solder printed circuit boards for consumer use and industrial printed circuit boards are used to form images by developing after UV irradiation and finish curing by heat and / or light irradiation (A liquid development type photo solder resist that is fully cured) is used.
- a liquid development type photo solder resist that is fully cured is used.
- solder resist workability and higher performance in response to the increase in the density of printed wiring boards accompanying the reduction in size and size of electronic equipment.
- an alkali development type using a dilute alkaline aqueous solution as a developing solution has become the mainstream in consideration of environmental problems, and is used in large quantities in the actual production of printed wiring boards.
- an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used.
- Patent Document 1 discloses a solder resist composition
- 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. It is disclosed.
- (meth) acrylic acid is added to an epoxy resin obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and a monohydric phenol, and then a polybasic carboxylic acid or anhydride thereof is added.
- a solder resist composition comprising a photosensitive resin obtained by reacting a product, a photopolymerization initiator, an organic solvent and the like is disclosed.
- conventional alkali development type photo solder resists are not necessarily sufficient in terms of durability, such as alkali resistance, water resistance, heat resistance, etc., compared with conventional thermosetting type and solvent development type. was there.
- a conventional alkali development type photo solder resist cracks may occur in the coating film due to thermal shock, or the coating film may be peeled off from the substrate or the sealing material.
- the alkali-developable photo solder resist has a hydrophilic group as a main component for imparting alkali developability, and such a hydrophilic group has a chemical solution, water, water vapor, etc. for the cured product. This is thought to be due to the fact that it may cause penetration and reduce the chemical resistance such as alkali resistance and the adhesion between the resist film and copper.
- semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package) are required to have high heat and heat resistance, but current alkali development type photo solder resists are used under high humidity and high temperatures. It can be said that there is still room for improvement even when looking at the numerical values in the PCT (pressure cooker test) performed in 1) and the HAST (highly accelerated life test) test performed by applying voltage under high temperature humidification conditions.
- PCT pressure cooker test
- HAST highly accelerated life test
- an object of the present invention is to provide an alkali-developable photo-curing property that has excellent thermal shock resistance and can form a cured film having excellent PCT resistance, HAST resistance, and electroless gold plating resistance, which is important as a solder resist for semiconductor packages.
- the object is to provide a thermosetting resin composition.
- the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product.
- An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.
- the alkali-developable photocurable thermosetting resin composition of the present invention comprises (A) a photosensitive carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a block copolymer, and (D ) It contains a thermosetting component.
- the alkali-developable photocurable thermosetting resin composition of the present invention preferably contains an epoxy resin as the component (D).
- the alkali-developable photo-curable thermosetting resin composition of the present invention is preferably such that the component (A) does not use an epoxy resin as a starting material.
- the component (A) preferably does not contain a hydroxyl group.
- the alkali-developable photo-curable thermosetting resin composition of the present invention is a resin in which the component (A) is a resin in which part or all of the phenolic hydroxyl group of the phenol resin is converted to an oxyalkyl group having an alcoholic hydroxyl group. Further, it is preferable that the product is obtained by reacting an ⁇ , ⁇ -ethylenically unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.
- the alkali-developable photo-curable thermosetting resin composition of the present invention has the (C) block copolymer represented by the following formula (I), ABA (I) (In the formula, A is a polymer unit having a glass transition point Tg of 0 ° C. or more, and B is a polymer unit having a glass transition point Tg of less than 0 ° C.) It is preferable that it is a block copolymer represented by these.
- the alkali-developable photo-curable thermosetting resin composition of the present invention is the above (C) block copolymer, wherein A is polystyrene, polyglycidyl methacrylate, or N-substituted in the formula (I).
- the block copolymer is preferably polyacrylamide, polymethyl methacrylate, a carboxylic acid-modified product or a hydrophilic group-modified product thereof, and B is polybutyl acrylate or polybutadiene.
- the photocurable thermosetting dry film of the present invention is obtained by applying and drying the above-described photocurable thermosetting resin composition on a carrier film.
- the cured product of the present invention is obtained by curing the above-mentioned photocurable thermosetting resin composition or photocurable thermosetting dry film by irradiation with active energy rays and / or heating. It is.
- the printed wiring board of the present invention is characterized by comprising the above cured product.
- thermosetting resin composition capable of alkali development capable of forming a cured film excellent in thermal shock resistance, PCT resistance, HAST resistance, and electroless gold plating resistance.
- the alkali-developable photocurable thermosetting resin composition of the present invention (hereinafter also referred to as a photocurable resin composition) comprises (A) a photosensitive carboxyl group-containing resin, (B) a photopolymerization initiator, (C It comprises a block copolymer and (D) a thermosetting component.
- a photocurable resin composition comprises (A) a photosensitive carboxyl group-containing resin, (B) a photopolymerization initiator, (C It comprises a block copolymer and (D) a thermosetting component.
- (A) Carboxyl group-containing resin As said (A) carboxyl group containing resin, resin containing a well-known carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. In addition to the carboxyl group, it is preferable to have an ethylenically unsaturated bond in the molecule from the viewpoint of photocurability and development resistance, but only a carboxyl group-containing resin having no ethylenically unsaturated double bond. Can also be used as component (A).
- component (A) When the resin of component (A) does not have an ethylenically unsaturated bond, a compound having at least one ethylenically unsaturated group in the molecule (photopolymerizable monomer) in order to make the composition photocurable Need to be used together.
- the ethylenically unsaturated double bond those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.
- the component (A) it is preferable to use a carboxyl group-containing resin that does not use an epoxy resin as a starting material.
- a carboxyl group-containing resin that does not use an epoxy resin as a starting material has a very low halide ion content, and can suppress deterioration in insulation reliability.
- (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain.
- a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and the resulting hydroxyl group is dibasic acid anhydride.
- a carboxyl group-containing photosensitive resin to which a product is added.
- An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like.
- Polybasic such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated carboxylic acid containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.
- Two or more per molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Reaction obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
- an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid
- a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide
- an alkylene oxide such as ethylene oxide or propylene oxide
- a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid.
- 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.
- a carboxyl group-containing urethane resin by a polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate
- a carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.
- a carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.
- 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.
- an unsaturated carboxylic acid such as (meth) acrylic acid
- an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- a carboxyl group formed by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate to the polyester resin Contains photosensitive resin.
- a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resin of any one of (1) to (10) described above.
- (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions below.
- carboxyl group-containing resins as described above, a carboxyl group-containing resin not using an epoxy resin as a starting material can be suitably used. Therefore, among the specific examples of the carboxyl group-containing resin described above, any one or more of the carboxyl group-containing resins (4) to (8) can be particularly preferably used.
- the amount of chlorine ion impurities can be suppressed to a very low value, for example, 100 ppm or less.
- the chloride ion content of the carboxyl group-containing resin suitably used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.
- a carboxyl group-containing urethane resin synthesized from an isocyanate compound not using phosgene as a starting material and a raw material not using epihalohydrin and having a chlorine ion impurity amount of 0 to 30 ppm is also preferably used.
- a resin containing no hydroxyl group can be easily synthesized by combining the equivalents of the hydroxyl group and the isocyanate group.
- an epoxy acrylate-modified raw material can be used as a diol compound in the synthesis of a urethane resin.
- chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.
- the above-mentioned carboxyl group-containing resins (4) to (8) Any one or more of these carboxyl group-containing resins can be used more suitably.
- the (A) carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, and therefore can be developed with an aqueous alkaline solution.
- the acid value of the (A) carboxyl group-containing resin used in the present invention is preferably 40 to 150 mgKOH / g.
- the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development may be difficult.
- it exceeds 150 mgKOH / g dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary, and in some cases, dissolution and peeling occur with the developer without distinguishing between the exposed portion and the unexposed portion, It may be difficult to draw a normal resist pattern. More preferably, it is 50 to 130 mgKOH / g.
- the weight average molecular weight of the (A) carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000.
- weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior.
- weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is 5,000 to 100,000.
- the blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass in the entire composition. When it is less than 20% by mass, the coating film strength may be lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the applicability and the like may decrease. More preferably, it is 30 to 50% by mass.
- (B) Photopolymerization initiator As the (B) photopolymerization initiator used in the present invention, any known photopolymerization initiator can be used, and among them, an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator. An acylphosphine oxide photopolymerization initiator is preferred.
- a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
- oxime ester photopolymerization initiators examples include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919, Adeka Arcles (registered trademark) NCI-831, manufactured by BASF Japan. Etc.
- numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
- X is 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, an alkoxy group having 1 to 8 carbon atoms).
- Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group.
- X and Y are each a methyl group or an ethyl group
- Z is methyl or phenyl
- n is 0, and
- Ar is phenylene, naphthylene, thiophene or thienylene. Photoinitiators are preferred.
- the blending amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If it is less than 0.01 part by mass, the photocurability on copper is insufficient, the coating film peels off, and the coating properties such as chemical resistance may be deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- ⁇ -aminoacetophenone photopolymerization initiator examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned.
- Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
- examples of commercially available products include Lucillin (registered trademark) TPO, Irgacure 819 manufactured by BASF Japan.
- the blending amount is 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance may deteriorate.
- it exceeds 15 parts by mass, a sufficient effect of reducing the outgas cannot be obtained, and light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- Irgacure 389 and Irgacure 784 manufactured by BASF Japan can also be suitably used.
- Photoinitiator or sensitizer In addition to the photopolymerization initiator, a photoinitiator or sensitizer can be suitably used for the photocurable resin composition of the present invention.
- the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as (B) a photopolymerization initiator, but are preferably used in combination with (B) a photopolymerization initiator.
- a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
- anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
- thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
- ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
- benzophenone compound examples include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like.
- a compound having a dialkylaminobenzene structure for example, 4,4′-dimethylaminobenzophenone (Nissoure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.), 4,4 Dialkylaminobenzophenone such as' -diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
- Dialkylamino group-containing coumarin compound ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethyl Aminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Nippon Kayaku Co., Ltd.
- a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
- a dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
- the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to obtain a solder resist film.
- 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
- thioxanthone compounds and tertiary amine compounds are preferred.
- a thioxanthone compound it is possible to improve deep curability.
- the amount of the photoinitiator or sensitizer used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the blending amount of the photoinitiator assistant or sensitizer is less than 0.1 parts by mass, a sufficient sensitizing effect tends to be not obtained.
- the amount exceeds 20 parts by mass light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing resin.
- the total amount of the photopolymerization initiator, the photoinitiator assistant, and the sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
- these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.
- the photocurable resin composition of the present invention contains (C) a block copolymer.
- a block copolymer generally refers to a copolymer having a molecular structure in which two or more types of polymers having different properties are connected by covalent bonds to form a long chain.
- the block copolymer used in the present invention is preferably an ABA or ABA ′ type block copolymer.
- the central B is a soft block and has a low glass transition point Tg, preferably less than 0 ° C.
- both outer sides A to A ′ are hard blocks and have a high Tg.
- Tg is measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- a to A ′ are composed of polymer units having a Tg of 50 ° C.
- a to A ′ are preferably those having high compatibility with the (A) carboxyl group-containing resin, and B is compatible with the (A) carboxyl group-containing resin. Those having low solubility are preferred. Thus, it is considered that a specific structure in the matrix can be easily shown by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.
- a or A ′ component polymethyl methacrylate (PMMA), polystyrene (PS) or the like is preferable, and as the B component, poly n-butyl acrylate (PBA), polybutadiene (PB) or the like is preferable.
- PMMA polymethyl methacrylate
- PBA poly n-butyl acrylate
- PB polybutadiene
- Compatibility unit can be introduced to further improve the compatibility.
- the block copolymer thus obtained has particularly good compatibility with the carboxyl group-containing resin. Surprisingly, the thermal shock resistance can be improved. Surprisingly, the material to which the elastomer is added tends to lower the glass transition temperature (Tg), whereas the material to which the block copolymer is added. Since Tg tends not to decrease, the block copolymer can be preferably used.
- Tg glass transition temperature
- Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application Nos. 2005-515281 and 2007-516326.
- Examples of commercially available block copolymers include acrylic triblock copolymers manufactured using living polymerization manufactured by Arkema.
- SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate
- MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate
- MAM N type treated with carboxylic acid modification or hydrophilic group modification.
- MAM A type examples include E41, E40, E21, E20, MAM types include M51, M52, M53, M22, etc.
- MAM N types include 52N, 22N, and MAM A types include SM4032XM10. It is done.
- the clarity produced by Kuraray is also a block copolymer derived from methyl methacrylate and butyl acrylate.
- the block copolymer used in the present invention is preferably a ternary or more block copolymer, and a block copolymer having a precisely controlled molecular structure synthesized by a living polymerization method is effective for obtaining the effects of the present invention. More preferred. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified.
- the molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.
- the weight average molecular weight of the block copolymer is generally in the range of 20,000 to 400,000, more preferably 30,000 to 300,000.
- weight average molecular weight is less than 20,000, the intended effects of toughness and flexibility cannot be obtained, and the tackiness is inferior.
- weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition is increased, and the printability and developability are significantly deteriorated.
- the blending amount of the block copolymer is preferably in the range of 1 to 50 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If it is less than 1 part by mass, the effect is not expected, and if it is 50 parts by mass or more, the photocurable resin composition is unfavorable because developability and applicability may be deteriorated.
- the photocurable resin composition of the present invention includes (D) a thermosetting component used for the purpose of improving characteristics such as heat resistance and insulation reliability.
- a thermosetting component used for the purpose of improving characteristics such as heat resistance and insulation reliability.
- thermosetting components such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc.
- the thermosetting resin can be used.
- thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.
- cyclic (thio) ether groups cyclic thioether groups
- thermosetting components having a cyclic (thio) ether group there are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
- the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes a plurality of either one of the three-, four- or five-membered cyclic ether groups, or the cyclic thioether group, or two kinds of groups in the molecule.
- a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound
- a compound having a plurality of oxetanyl groups in the molecule that is, a polyfunctional oxetane compound
- thioether groups in the molecule examples thereof include compounds, that is, episulfide resins.
- polyfunctional epoxy compound examples include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330, A.I. E. R.
- Type or biphenol type epoxy resin or a mixture thereof bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical; TEPIC etc.
- bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .
- Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation
- tetraphenylolethane type epoxy resin such
- epoxy resins manufactured by DIC, EXA-4816, EXA-4822, EXA-4850 series flexible tough epoxy resin; Examples include, but are not limited to, glycidyl methacrylate copolymer epoxy resins such as ⁇ 50S and CP-50M; and cyclohexyl maleimide / glycidyl methacrylate copolymer epoxy resins. These epoxy resins can be used alone or in combination of two or more.
- polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
- polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
- Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
- the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). More preferably, it is in the range of 0.5 to 2.0 equivalents.
- the amount of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.3 equivalents, carboxyl groups remain in the cured film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. This is not preferable.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dried coating film, which is not preferable because the strength of the cured coating film may be reduced.
- thermosetting component having a plurality of cyclic (thio) ether groups in the molecule
- thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
- Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
- Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, 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.
- thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
- thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. 15.0 parts by mass.
- amino resin examples include amino resins such as melamine derivatives and benzoguanamine derivatives.
- examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
- the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
- the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
- a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
- Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, and the like. 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (made by Sanwa Chemical Co., Ltd.).
- the isocyanate compound a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used.
- the polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
- aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
- alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
- adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
- the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily inactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
- the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
- an isocyanate compound used in order to synthesize combine a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example.
- aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
- isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime
- the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
- Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B 846, B-870, B-874, B-882 (Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
- the blending amount of the polyisocyanate compound or the blocked isocyanate compound is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is less than 1 part by mass, sufficient toughness of the coating film may not be obtained, which is not preferable.
- the amount exceeds 100 parts by mass the storage stability may decrease, which is not preferable.
- a urethanization catalyst can be added to the photocurable resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups and isocyanate groups.
- the urethanization catalyst one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts should be used. Is preferred.
- tin catalyst examples include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
- metal chloride examples include metal chlorides selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al.
- metal chlorides selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al.
- cobalt chloride, nickel chloride, ferric chloride, and the like. Can be mentioned.
- the metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al.
- metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al.
- cobalt acetylacetonate, nickel acetylacetonate, iron acetyl Examples include acetonate.
- the metal sulfate is a metal sulfate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include copper sulfate.
- Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′.
- N ′′, N ′′ -pentamethyldiethylenetriamine N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxy Chill) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N, N, N′-trimethyl
- amine salt examples include organic acid salt amine salts such as DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).
- the blending amount of the urethanization catalyst is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the photocurable resin composition of this invention can mix
- known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
- red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
- -Indexes (CI .: The Society of Dyers and Colorists) issued with the number.
- Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12,14, 15, 16, 17, 21, 22, 23,31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188,193, 210, 245, 253, 258,266, 267, 268, 269.
- Disazo Pigment Red 37, 38, 41.
- Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2,53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
- Benzimidazolone series Pigment Red 171, 175, 176, 185, 208.
- Perylene series Solvent Red 135, 179, Pigment Red 123,149, 166, 178, 179, 190, 194,224.
- Diketopyrrolopyrrole type Pigment Red 254, 255, 264, 270, 272.
- Condensed azo series Pigment Red 220, 144, 166, 214, 220, 221,242.
- Anthraquinone series Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207.
- Quinacridone series Pigment Red 122, 202, 206, 207, 209.
- Blue colorant include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically, Pigment Blue 15, 15: 1 , 15: 2, 15: 3, 15: 4, 15: 6,16, 60.
- Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used as the dye system.
- a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Green colorant includes phthalocyanine series, anthraquinone series, and perylene series. Specifically, PigmentGreen 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
- Anthraquinone series Solvent Yellow 163, Pigment Yellow 24,108, 193, 147, 199, 202.
- Isoindolinone series Pigment Yellow 110, 109, 139, 179, 185.
- Condensed azo type Pigment Yellow 93, 94, 95, 128, 155, 166,180.
- Benzimidazolone series Pigment Yellow 120, 151, 154, 156, 175, 181.
- Monoazo Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10,12, 61, 62, 62: 1, 65, 73,74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169,182, 183.
- Disazo type Pigment Yellow 12, 13, 14, 16, 17, 55, 63,81, 83, 87, 126, 127,152, 170, 172, 174, 176, 188, 198.
- a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
- a colorant such as purple, orange, brown, or black
- the mixing ratio of these colorants is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. is there.
- Photopolymerizable monomer In the present invention, a compound (photopolymerizable monomer) having one or more ethylenically unsaturated groups can be used.
- the photopolymerizable monomer is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the (A) carboxyl group-containing resin in an alkaline aqueous solution.
- Examples of the compound used as the photopolymerizable monomer in the present invention include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. It is done.
- 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-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Multivalent acrylates such as a peroxide adduct, a propylene oxide adduct, or an ⁇ -caprolactone ad
- 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.
- An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photopolymerizable monomer.
- Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
- the compounding amount of the compound having one or more ethylenically unsaturated groups in the molecule used as the photopolymerizable monomer is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. More preferably, the proportion is 5 to 70 parts by mass.
- the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern development may be difficult due to alkali development after irradiation with active energy rays, which is not preferable.
- the amount exceeds 100 parts by mass the solubility in an aqueous alkali solution is lowered, and the coating film may become brittle.
- the photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the obtained cured product.
- a filler publicly known and commonly used inorganic or organic fillers can be used.
- barium sulfate, spherical silica, Neuburg silica clay particles, and talc are preferably used.
- aluminum hydroxide, magnesium hydroxide, boehmite and the like can also be used.
- NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano-silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin.
- XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names)
- Hanose-Chemie NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) can also be used. .
- the photocurable resin composition of the present invention preferably further contains a filler having a refractive index in the range of 1.45 to 1.65 because of its excellent light transmittance. More preferably, it is in the range of 1.50 to 1.65.
- the blending amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Part.
- the blending amount of the filler exceeds 500 parts by mass, the viscosity of the photocurable resin composition becomes high and printability may be lowered, or the cured product may become brittle, which is not preferable.
- Binder polymer Conventionally known binder polymers can be used in the photocurable resin composition of the present invention for the purpose of improving the flexibility and dryness of the cured product obtained.
- the binder polymer cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable.
- the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo Co., Ltd., and a phenoxy resin-based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.
- the amount of the binder polymer added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the photocurable resin composition is not preferable because the alkali developability of the photocurable resin composition is poor and the usable potable time may be shortened.
- the photocurable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the resulting cured product and improving the brittleness of the cured product.
- the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers.
- resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
- epoxy-containing polybutadiene elastomers acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used.
- One type of elastomer may be used alone, or a mixture of two or more types may be used.
- the photocurable resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, and hydrotalcite, if necessary.
- a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, and hydrotalcite, if necessary.
- Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
- Known and conventional additives such as copper damage prevention agents such as those based on triazine and triazine thiols can be blended.
- the photo-curable resin composition of the present invention further contains known and commonly used additives such as a chain transfer agent, a rust inhibitor, an adhesion promoter, an antioxidant, a polymerization inhibitor, and an ultraviolet absorber as necessary. Can be blended.
- the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the above (A) carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. can do.
- organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, 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 a
- the photocurable resin composition of the present invention can also be in the form of a dry film comprising a carrier film (support) and a layer made of the photocurable resin composition formed on the carrier film.
- the photocurable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll.
- a film can be obtained by applying a uniform thickness on a carrier film with a coater, gravure coater, spray coater or the like, and drying usually 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 is appropriately selected in the range of 5 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
- a plastic film As the carrier film, a plastic film is 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 cover film that can be peeled is laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
- a cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
- the photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method.
- a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C., followed by volatile drying (temporary drying). Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, the photocurable resin composition layer was laminated on the base material by a laminator or the like so as to come into contact with the base material. Thereafter, the resin insulating layer can be formed by peeling off the carrier film.
- Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) using other materials such as epoxy, fluorine, polyethylene, PPO, cyanate ester, etc., and other polyimide films, PET films Glass substrate, ceramic substrate, wafer plate and the like.
- Volatile drying performed after the photocurable resin composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (with a heat source of an air heating method using steam) It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.
- an exposed portion irradiated with active energy rays. Part
- a contact type or non-contact type
- exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3).
- a resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution).
- the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
- the laser light source of the direct drawing machine either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Exposure for image formation depends thickness, etc., but generally 20 ⁇ 800mJ / cm 2, preferably be in the range of 20 ⁇ 600mJ / cm 2.
- the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%.
- triphenylphosphine was charged, heated to 110 ° C., reacted for 2 hours, heated to 120 ° C., and further reacted for 12 hours.
- 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged, reacted at 110 ° C. for 4 hours, and cooled.
- varnish A-2 a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained.
- this is referred to as varnish A-2.
- Varnish BC-3 50 g of carbitol acetate was added to 15 g of MAM N type block copolymer M22N subjected to hydrophilic treatment, and the mixture was stirred and heated at 85 ° C. to dissolve (solid content: 23.1%).
- Varnish BC-4 To 15 g of MAM type block copolymer M51, 50 g of carbitol acetate was added, stirred and dissolved by heating at 85 ° C. (solid content: 23.1%).
- Varnish BC-5 To 15 g of MAM type block copolymer M22, 50 g of carbitol acetate was added, stirred and dissolved by heating at 85 ° C. (solid content: 23.1%).
- Varnish BC-6 To 15 g of MAM type block copolymer M22, 50 g of carbitol acetate was added, stirred and dissolved by heating at 85 ° C. (solid content: 23.1%).
- Examples 1 to 9 and Comparative Examples 1 to 3 The resin solution (varnish) of the above synthesis example was blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, kneaded with a three-roll mill, and light A curable resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.
- ⁇ Maximum development life> The compositions of Examples and Comparative Examples shown in Table 1 were applied on the entire surface of the patterned copper foil substrate so as to have a dry film thickness of about 20 ⁇ m by screen printing, and dried at 80 ° C. for 10 minutes from 20 minutes to 80 minutes. The substrate was taken out every minute and allowed to cool to room temperature. This substrate was developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which a dry coating film did not remain was judged as the maximum development life.
- This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
- the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
- ⁇ Acid resistance> The evaluation substrate was immersed in a 10% by volume H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to the tape peel was confirmed. ⁇ : No change is observed. ⁇ : Slightly changed. X: The coating film has swelling or swelling dropping.
- the evaluation substrate subjected to plating was evaluated for the presence or absence of peeling of the resist layer and the presence or absence of penetration of the plating, and then the presence or absence of peeling of the resist layer was evaluated by tape peeling.
- the judgment criteria are as follows. ⁇ : No soaking or whitening is observed after plating, and no peeling occurs after tape peeling. ⁇ : Permeation and whitening are confirmed after plating, but there is no peeling after tape peeling. X: Permeation and whitening were confirmed after plating, and peeling occurred after tape peeling.
- PCT resistance Similar to the evaluation of electroless gold plating resistance, various evaluation substrates subjected to electroless gold plating can be used under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec). PCT resistance was evaluated according to the state of the coating film. The judgment criteria are as follows. A: No swelling, peeling, discoloration, or elution even after 240 hours of testing. ⁇ : No swelling, peeling, discoloration or dissolution after 168 hours test, but any swelling, peeling, discoloration or dissolution after 240 hours. X: Swelling, peeling, discoloration, and elution are observed during the 168 hour test.
- Examples 10 to 18 and Comparative Examples 4 to 6 The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 prepared at the blending ratios shown in Table 1 were diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, and a thickness of 20 ⁇ m. A photocurable resin composition layer was formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 10 to 18 and Comparative Examples 4 to 6, respectively. It should be noted that Examples 1 to 9 and Comparative Examples were such that the dry film using the resin composition of Example 1 was Example 10, and the dry film using the resin composition of Example 2 was Example 11. The compositions of 1 to 3, the dry films of Examples 10 to 18, and Comparative Examples 4 to 6 correspond in order.
- ⁇ Dry film evaluation> The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then, under the same conditions as the substrate used for the coating film property evaluation of the above example. Exposed. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.
- the cured product obtained from the photocurable resin composition according to the present invention which contains a block copolymer, has acid resistance, alkali resistance, solder heat resistance, and electroless resistance. It was excellent in plating property, PCT resistance, thermal shock resistance and HAST characteristics. On the other hand, the hardened
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Abstract
Description
さらに本発明の目的は、このような光硬化性熱硬化性樹脂組成物を用いることによって得られる上記のような諸特性に優れたドライフィルム及び硬化物、並びに該ドライフィルムや硬化物によりソルダーレジスト等の硬化被膜が形成されてなるプリント配線板を提供することにある。
A-B-A (I)
(式中、Aはガラス転移点Tgが0℃以上のポリマー単位であり、Bはガラス転移点Tgが0℃未満のポリマー単位である。)
で表されるブロック共重合体であることが好ましい。
以下、本発明の光硬化性樹脂組成物の各構成成分について詳しく説明する。
上記(A)カルボキシル基含有樹脂としては、公知のカルボキシル基を含む樹脂を用いることができる。カルボキシル基の存在により、樹脂組成物をアルカリ現像性とすることができる。また、光硬化性や耐現像性の観点から、カルボキシル基の他に、分子内にエチレン性不飽和結合を有することが好ましいが、エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを(A)成分として用いることもできる。(A)成分の樹脂がエチレン性不飽和結合を有さない場合は、組成物を光硬化性とするために分子中に1個以上のエチレン性不飽和基を有する化合物(光重合性モノマー)を併用する必要がある。エチレン性不飽和二重結合としては、アクリル酸もしくはメタアクリル酸又はそれらの誘導体由来のものが好ましい。
また、(A)成分として、エポキシ樹脂を出発原料として使用していないカルボキシル基含有樹脂を用いることが好ましい。エポキシ樹脂を出発原料として使用していないカルボキシル基含有樹脂は、ハロゲン化物イオン含有量が非常に少なく、絶縁信頼性の劣化を抑えることができる。
(2)後述するような2官能(固形)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。
(3)1分子中に2個以上のエポキシ基を有するエポキシ化合物に、1分子中に少なくとも1個のアルコール性水酸基と1個のフェノール性水酸基を有する化合物と、(メタ)アクリル酸などの不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、アジピン酸などの多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(4)ビスフェノールA、ビスフェノールF、ビスフェノールS、ノボラック型フェノール樹脂、ポリ-p-ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物などの1分子中に2個以上のフェノール性水酸基を有する化合物と、エチレンオキシド、プロピレンオキシドなどのアルキレンオキシドとを反応させて得られる反応生成物に、(メタ)アクリル酸などの不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(5)1分子中に2個以上のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネートなどの環状カーボネート化合物とを反応させて得られる反応生成物に、不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(6)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及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。
(7)ジイソシアネートと、ジメチロールプロピオン酸、ジメチロール酪酸などのカルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、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ウレタン樹脂。
(8)ジイソシアネートと、カルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、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ウレタン樹脂。
(9)(メタ)アクリル酸などの不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレンなどの不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。
(10)後述するような多官能オキセタン樹脂に、アジピン酸、フタル酸、ヘキサヒドロフタル酸などのジカルボン酸を反応させ、生じた1級の水酸基に、2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂に、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1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。
(11)上述した(1)~(10)のいずれかのカルボキシル基含有樹脂に、1分子中に環状エーテル基と(メタ)アクリロイル基を有する化合物を付加させたカルボキシル基含有感光性樹脂。
本発明において用いられる(B)光重合開始剤としては、公知のいずれのものも用いることができるが、中でも、オキシムエステル基を有するオキシムエステル系光重合開始剤、α-アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤が好ましい。(B)光重合開始剤は1種を単独で用いてもよく、2種以上を併用して用いてもよい。
(式中、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又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又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又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又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、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-ジイルを表し、nは0又は1の整数である)
(B)光重合開始剤の他、本発明の光硬化性樹脂組成物には、光開始助剤または増感剤を好適に用いることができる。光開始助剤または増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、3級アミン化合物、及びキサントン化合物などを挙げることができる。これらの化合物は、(B)光重合開始剤として用いることができる場合もあるが、(B)光重合開始剤と併用して用いることが好ましい。また、光開始助剤または増感剤は1種類を単独で用いてもよく、2種以上を併用してもよい。
ジアルキルアミノベンゾフェノン化合物としては、4,4’-ジエチルアミノベンゾフェノンが毒性が低いことから好ましい。ジアルキルアミノ基含有クマリン化合物は、最大吸収波長が350~410nmと紫外線領域にあるため、着色が少なく、無色透明な感光性組成物はもとより、着色顔料を用い、着色顔料自体の色を反映した着色ソルダーレジスト膜を得ることが可能となる。特に、7-(ジエチルアミノ)-4-メチル-2H-1-ベンゾピラン-2-オンが、波長400~410nmのレーザー光に対して優れた増感効果を示すことから好ましい。
本発明の光硬化性樹脂組成物には、(C)ブロック共重合体が含まれる。ブロック共重合体とは一般的に性質の異なる二種類以上のポリマーが、共有結合で繋がり長い連鎖になった分子構造の共重合体を呼ぶ。
また、ABAあるいはABA’型ブロック共重合体のうち、AないしA’がTgが50℃以上のポリマー単位からなり、BがTgが-20℃以下であるポリマー単位からなるブロック共重合体がさらに好ましい。
また、ABAあるいはABA’型ブロック共重合体のうち、AないしA’が上記(A)カルボキシル基含有樹脂との相溶性が高いものが好ましく、Bが上記(A)カルボキシル基含有樹脂との相溶性が低いものが好ましい。このように、両端のブロックがマトリックスに相溶であり、中央のブロックがマトリックスに不相溶であるブロック共重合体とすることで、マトリックス中において特異的な構造を示しやすくなると考えられる。
また、クラレ社製のクラリティもメタクリル酸メチルとアクリル酸ブチルより誘導されるブロック共重合である。
本発明の光硬化性樹脂組成物は、耐熱性、絶縁信頼性等の特性を向上させる目的で用いられる(D)熱硬化性成分を含む。(D)熱硬化性成分としては、イソシアネート化合物、ブロックイソシアネート化合物、アミノ樹脂、マレイミド化合物、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、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などの公知慣用の熱硬化性樹脂が使用できる。これらの中でも好ましい熱硬化性成分は、1分子中に複数の環状エーテル基及び/又は環状チオエーテル基(以下、環状(チオ)エーテル基と略称する)を有する熱硬化性成分である。これら環状(チオ)エーテル基を有する熱硬化性成分は、市販されている種類が多く、その構造によって多様な特性を付与することができる。
本発明の光硬化性樹脂組成物は、着色剤を配合することができる。着色剤としては、赤、青、緑、黄などの公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しないことが好ましい。
ジスアゾ系:Pigment Red 37, 38, 41。
モノアゾレーキ系:Pigment Red 48:1, 48:2, 48:3, 48:4,49:1, 49:2, 50:1, 52:1, 52:2,53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68。
ぺリレン系:Solvent Red 135, 179, Pigment Red 123,149, 166, 178, 179, 190, 194,224。
ジケトピロロピロール系:Pigment Red 254, 255, 264, 270, 272。
縮合アゾ系:Pigment Red 220, 144, 166, 214, 220, 221,242。
アンスラキノン系:Pigment Red 168, 177, 216、Solvent Red 149,150, 52, 207。
キナクリドン系:Pigment Red 122, 202, 206, 207, 209。
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には、下記のようなものを挙げることができる:Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6,16, 60。染料系としては、Solvent Blue 35, 63, 68, 70, 83, 87, 94,97, 122, 136, 67, 70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigmentGreen 7, 36、Solvent Green 3, 5, 20,28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
アントラキノン系:Solvent Yellow 163, Pigment Yellow 24,108, 193, 147, 199, 202。
イソインドリノン系:Pigment Yellow 110, 109, 139, 179, 185。
縮合アゾ系:Pigment Yellow 93, 94, 95, 128, 155, 166,180。
モノアゾ系:Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10,12, 61, 62, 62:1, 65, 73,74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169,182, 183。
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63,81, 83, 87, 126, 127,152, 170, 172, 174, 176, 188, 198。
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet13, 36、C.I. Pigment Orange 1,5, 13, 14, 16, 17, 24,34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73、PigmentBrown 23, 25, Pigment Black 1, 7等がある。
本発明において、1個以上のエチレン性不飽和基を有する化合物(光重合性モノマー)を用いることができる。光重合性モノマーは、活性エネルギー線照射により、光硬化して、前記(A)カルボキシル基含有樹脂を、アルカリ水溶液に不溶化、又は不溶化を助けるものである。
本発明の光硬化性樹脂組成物は、得られる硬化物の物理的強度等を上げるために、必要に応じて、フィラーを配合することができる。このようなフィラーとしては、公知慣用の無機又は有機フィラーが使用できるが、特に硫酸バリウム、球状シリカ、ノイブルグ珪土粒子、及びタルクが好ましく用いられる。また、難燃性を付与する目的で、水酸化アルミニウム、水酸化マグネシウム、ベーマイトなども使用することができる。さらに、1個以上のエチレン性不飽和基を有する化合物や前記多官能エポキシ樹脂にナノシリカを分散したHanse-Chemie社製のNANOCRYL(商品名) XP 0396、XP 0596、XP 0733、XP 0746、XP 0765、XP 0768、XP 0953、XP 0954、XP 1045(何れも製品グレード名)や、Hanse-Chemie社製のNANOPOX(商品名) XP 0516、XP 0525、XP 0314(何れも製品グレード名)も使用できる。これらを単独で又は2種以上配合することができる。
また本発明の光硬化性樹脂組成物は、さらに、光透過性に優れることより、屈折率が1.45~1.65の範囲にあるフィラーを含むことが好ましい。より好ましくは、1.50~1.65の範囲である。
本発明の光硬化性樹脂組成物には得られる硬化物の可撓性、指触乾燥性の向上を目的に慣用公知のバインダーポリマーを使用することができる。バインダーポリマーとしてはセルロース系、ポリエステル系、フェノキシ樹脂系ポリマーが好ましい。セルロース系ポリマーとしてはイーストマン社製セルロースアセテートブチレート(CAB)、セルロースアセテートプロピオネート(CAP)シリーズが挙げられ、ポリエステル系ポリマーとしては東洋紡社製バイロンシリーズ、フェノキシ樹脂系ポリマーとしてはビスフェノールA、ビスフェノールFおよびそれらの水添化合物のフェノキシ樹脂が好ましい。
本発明の光硬化性樹脂組成物は、得られる硬化物に対する柔軟性の付与、硬化物の脆さの改善などを目的にエラストマーを配合することができる。エラストマーとしては、例えばポリエステル系エラストマー、ポリウレタン系エラストマー、ポリエステルウレタン系エラストマー、ポリアミド系エラストマー、ポリエステルアミド系エラストマー、アクリル系エラストマー、オレフィン系エラストマーが挙げられる。また、種々の骨格を有するエポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン-アクリロニトリルゴムで変性した樹脂なども使用できる。更にはエポキシ含有ポリブタジエン系エラストマー、アクリル含有ポリブタジエン系エラストマー、水酸基含有ポリブタジエン系エラストマー、水酸基含有イソプレン系エラストマー等も使用することができる。エラストマーは、1種を単独で用いてもよく、2種類以上の混合物として使用してもよい。
本発明の光硬化性樹脂組成物は、さらに必要に応じて、連鎖移動剤、防錆剤、密着促進剤、酸化防止剤、重合禁止剤、紫外線吸収剤などのような公知慣用の添加剤類を配合することができる。
さらに、本発明の光硬化性樹脂組成物は、上記(A)カルボキシル基含有樹脂の合成や組成物の調整のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。
ドライフィルム化に際しては、本発明の光硬化性樹脂組成物を前記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分間乾燥して膜を得ることができる。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の範囲で適宜選択される。
剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。
[合成例1]
温度計、窒素導入装置兼アルキレンオキシド導入装置及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(昭和電工社製、ショウノール(登録商標)CRG951、OH当量:119.4)119.4g、水酸化カリウム1.19g及びトルエン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。
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(登録商標) 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)、及びハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。
MAMタイプのブロック共重合体M52 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-1とする。
親水性処理されたMAM Nタイプのブロック共重合体M52N 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-2とする。
MAMタイプのブロック共重合体M53 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-3とする。
親水性処理されたMAM Nタイプのブロック共重合体M22N 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-4とする。
MAMタイプのブロック共重合体M51 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-5とする。
MAMタイプのブロック共重合体M22 15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスBC-6とする。
三菱レイヨン社製BR-87(主成分:ポリメチルメタアクリレート、Mw:25,000)15gにカルビトールアセテート50gを加え、攪拌し、100℃にて加熱することにより溶解させた(固形分23.1%)。これをワニスC-1とする。
根上工業社製AS-3000E(主成分:ポリブチルアクリレート、Mw:650,000、固形分30%)を用いた。これをワニスC-2とする。
上記合成例の樹脂溶液(ワニス)を、下記表1に示す種々の成分と共に表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、光硬化性樹脂組成物を調製した。ここで、得られた感光性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ、15μm以下であった。
*2:2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(ルシリンTPO:BASFジャパン社製)
*3:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1,1-(O-アセチルオキシム)(イルガキュア OXE 02:BASFジャパン社製)
*4:ビフェニルノボラック型エポキシ樹脂(NC-3000HCA75:日本化薬社製)
*5:ビスフェノール型エポキシ樹脂(YSLV-80XY:東都化成社製)
*6:硫酸バリウム(堺化学工業社製)
*7:アドマファインSO-E2(アドマテックス社製)
*8:アクティジルAM(HOFFMANN MINERAL社製)
*9:C.I.Pigment Blue 15:3
*10:C.I.Pigment Yellow147
*11:2-メルカプトベンゾチアゾール
*12:IRGAFOS168:BASFジャパン社製
*13:IRGANOX1010:BASFジャパン社製
*14:ジエチレングリコールモノエチルエーテールアセテート
*15:ジペンタエリスリトールペンタアクリレート
<最適露光量>
銅厚18μmの回路パターン基板を銅表面粗化処理(メック社製メックエッチボンドCZ-8100)後、水洗し、乾燥した後、表1に示す実施例及び比較例の光硬化性樹脂組成物をスクリーン印刷法により全面に塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ、約20μmの乾燥塗膜を得た。その後、高圧水銀灯搭載の露光装置を用いてステップタブレット(Kodak No.2)を介して露光し、現像(30℃、0.2MPa、1%炭酸ナトリウム水溶液)を90秒で行った際残存するステップタブレットのパターンが7段の時を最適露光量とした。
表1に示す実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で乾燥膜厚約20μmになるように全面塗布し、80℃で乾燥し20分から80分まで10分おきに基板を取り出し、室温まで放冷した。この基板に30℃の1%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、乾燥塗膜が残らない最大許容乾燥時間を最大現像ライフとして判断した。
表1に示す実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で乾燥膜厚約20μmになるように全面塗布し、80℃で30分乾燥し、室温まで放冷した。この基板に高圧水銀灯を搭載した露光装置を用いて最適露光量でソルダーレジストパターンを露光し、30℃の1%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、レジストパターンを得た。この基板を、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、150℃で60分加熱して硬化した。得られたプリント基板(評価基板)に対して以下のように特性を評価した。
評価基板を10容量%H2SO4水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピールによる剥がれを確認した。
○:変化が認められないもの。
△:ほんの僅か変化しているもの。
×:塗膜に膨れあるいは膨潤脱落があるもの。
評価基板を10容量%NaOH水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピールによる剥がれを確認した。
○:変化が認められないもの。
△:ほんの僅か変化しているもの。
×:塗膜に膨れあるいは膨潤脱落があるもの。
ロジン系フラックスを塗布した評価基板を、予め260℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○:10秒間浸漬を3回以上繰り返しても剥がれが認められない。
△:10秒間浸漬を3回繰り返すと少し剥がれる。
×:10秒間浸漬を2回以内にレジスト層に膨れ、剥がれがある。
評価基板について、市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル5μm、金0.05μmの条件で無電解金めっき処理を行った。めっきを行った評価基板を、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
○:めっき後にしみ込み、白化が見られず、テープピーリング後に剥がれはない。
△:めっき後にしみ込み、白化が確認されるが、テープピーリング後の剥がれはない。
×:めっき後にしみ込み、白化が確認され、テープピーリング後に剥がれがある。
耐無電解金めっき性の評価と同様に無電解金めっきを施した評価基板を、PCT装置(エスペック社製HAST SYSTEM TPC-412MD)を用いて、121℃、飽和、0.2MPaの条件で種々の時間処理し、塗膜の状態によりPCT耐性を評価した。判定基準は以下のとおりである。
○:240時間試験を行っても、膨れ、剥がれ、変色、溶出のないもの。
△:168時間試験経過時、膨れ、剥がれ、変色、溶出はないが、240時間経過時、膨れ、剥がれ、変色、溶出のいずれかが見られるもの。
×:168時間試験経過時、膨れ、剥がれ、変色、溶出が見られるもの。
□抜き、○抜きパターンを形成したソルダーレジスト硬化塗膜を有する評価基板を作製した。得られた評価基板を冷熱衝撃試験器(エタック社製)で-55℃/30分~150℃/30分を1サイクルとして1000サイクルの耐性試験を行った。試験後、処理後の硬化膜を目視により観察し、クラックの発生状況を下記の基準にて判断した。
◎:クラック発生率10%未満
○:クラック発生率10~30%未満
△:クラック発生率30~50%
×:クラック発生率50%超
クシ型電極(ライン/スペース=30ミクロン/30ミクロン)が形成されたBT基板に、ソルダーレジスト硬化塗膜を形成し、評価基板を作成した。この評価基板を、130℃、湿度85%の雰囲気下の高温高湿槽に入れ、電圧5.5Vを荷電し、槽内HAST試験を行った。種々の時間経過時の槽内絶縁抵抗値を下記の判断基準に従い評価した。
○:240時間経過後、ショート発生は確認されず、抵抗値は108Ω以上
△:240時間経過後、ショート発生は確認されず、抵抗値は108Ω未満
×:ショート発生
表1に示す配合割合で調製した実施例1~9及び比較例1~3の各組成物をメチルエチルケトンにて希釈し、PETフィルム上に塗布して80℃で30分乾燥し、厚さ20μmの光硬化性樹脂組成物層を形成した。さらにその上にカバーフィルムを貼り合わせてドライフィルムを作製し、それぞれを実施例10~18及び比較例4~6とした。なお、実施例1の樹脂組成物を用いたドライフィルムを実施例10とし、実施例2の樹脂組成物を用いたドライフィルムを実施例11とするというように、実施例1~9、比較例1~3の組成と実施例10~18、比較例4~6のドライフィルムは、順に対応する。
上記のようにして得られたドライフィルムからカバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを熱ラミネートし、次いで、前記実施例の塗膜特性評価に用いた基板と同様の条件で露光した。露光後、キャリアフィルムを剥がし、30℃の1wt%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、レジストパターンを得た。この基板を、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、150℃で60分加熱して硬化した。得られた硬化被膜を有する試験基板について、前述した試験方法及び評価方法にて、各特性の評価試験を行った。結果を表3に示す。
Claims (9)
- (A)感光性カルボキシル基含有樹脂、
(B)光重合開始剤、
(C)ブロック共重合体、および、
(D)熱硬化性成分
を含有することを特徴とするアルカリ現像可能な光硬化性熱硬化性樹脂組成物。 - 前記(D)成分としてエポキシ樹脂を含有する請求項1記載のアルカリ現像可能な光硬化性熱硬化性樹脂組成物。
- 前記(A)成分がエポキシ樹脂を出発原料としないものである請求項1または2記載のアルカリ現像可能な光硬化性熱硬化性樹脂組成物。
- 前記(A)成分が水酸基を含有しないものである請求項1または2記載のアルカリ現像可能な光硬化性熱硬化性樹脂組成物。
- 前記(A)成分がフェノール樹脂のフェノール性水酸基の一部又は全部をアルコール性水酸基を有するオキシアルキル基に変換した樹脂に、α,β-エチレン性不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるものである請求項1または2記載のアルカリ現像可能な光硬化性熱硬化性樹脂組成物。
- 前記(C)ブロック共重合体が、下記式(I)、
A-B-A (I)
(式中、Aはガラス転移点Tgが0℃以上のポリマー単位であり、Bはガラス転移点Tgが0℃未満のポリマー単位である。)
で表されるブロック共重合体である請求項1または2記載のアルカリ現像可能な光硬化性熱硬化性樹脂組成物。 - 請求項1または2記載の光硬化性熱硬化性樹脂組成物を、キャリアフィルム上に塗布乾燥して得られることを特徴とする光硬化性熱硬化性ドライフィルム。
- 前記請求項1または2記載の光硬化性熱硬化性樹脂組成物、又は請求項7記載の光硬化性熱硬化性ドライフィルムを、活性エネルギー線照射及び/又は加熱により硬化させて得られることを特徴とする硬化物。
- 請求項8記載の硬化物を備えることを特徴とするプリント配線板。
Priority Applications (4)
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US14/127,078 US9310680B2 (en) | 2011-06-17 | 2012-06-15 | Photocurable/thermosetting resin composition |
KR1020147001332A KR101604557B1 (ko) | 2011-06-17 | 2012-06-15 | 광경화성 열경화성 수지 조성물 |
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US9310680B2 (en) | 2016-04-12 |
JP5847814B2 (ja) | 2016-01-27 |
US20140147776A1 (en) | 2014-05-29 |
KR101604557B1 (ko) | 2016-03-17 |
JPWO2012173242A1 (ja) | 2015-02-23 |
TW201313819A (zh) | 2013-04-01 |
TWI538952B (zh) | 2016-06-21 |
CN103492950A (zh) | 2014-01-01 |
KR20140029521A (ko) | 2014-03-10 |
CN103492950B (zh) | 2016-04-13 |
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