WO2014002294A1 - アルカリ現像型感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 - Google Patents
アルカリ現像型感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 Download PDFInfo
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- WO2014002294A1 WO2014002294A1 PCT/JP2012/070726 JP2012070726W WO2014002294A1 WO 2014002294 A1 WO2014002294 A1 WO 2014002294A1 JP 2012070726 W JP2012070726 W JP 2012070726W WO 2014002294 A1 WO2014002294 A1 WO 2014002294A1
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- photosensitive resin
- resin composition
- alkali
- developable photosensitive
- composition according
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
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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
-
- 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
-
- 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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline 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
- 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
-
- 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
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
-
- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
Definitions
- the present invention relates to an alkali-developable photosensitive resin composition, a dry film, a cured product, and a printed wiring board suitable for forming a solder resist or the like of a printed wiring board, in particular, without coarse particles, excellent in storage stability, working
- An alkali development type photosensitive resin composition capable of forming a pattern of an alkali development type photosensitive resin composition cured coating film that suppresses deterioration of the environment and has few harmful substances to the human body, the alkali development type photosensitive resin composition,
- the present invention relates to a dry film obtained by coating and drying on a carrier film, a cured product of the alkali-developable photosensitive composition or the dry film, and a printed wiring board provided with the cured product.
- solder resists for some consumer printed wiring boards and most industrial printed wiring boards are imaged by ultraviolet rays and developed from the viewpoint of high accuracy and high density.
- Liquid development type solder resist ink that is finish-cured (main-cured) is used.
- an alkali development type liquid solder resist ink using a dilute alkaline aqueous solution as a developing solution has become the mainstream.
- polybasic acid anhydride is used as a reaction product of a novolak epoxy compound and an unsaturated monocarboxylic acid as described in Patent Document 1.
- Liquid solder resist inks comprising an active energy ray-curable resin to which a product is added, a photopolymerization initiator, an organic solvent, a filling powder and an epoxy compound are widely used.
- the role of the photopolymerization initiator with respect to the solder resist is to serve as a starting point for the photocuring reaction during exposure.
- the photopolymerization initiator absorbs light during exposure and is activated and decomposed, and the activated photopolymerization initiator reacts with a photosensitive resin such as a monomer or an oligomer.
- the reacted photosensitive resin component undergoes a three-dimensional cross-linking reaction in a chain to increase the molecular weight and become a solid (cured).
- the photopolymerization initiator plays an important role for forming a solder resist.
- the solder resist ink is formed by mixing many components as described above and generally dispersing and forming with three rolls, and the compatibility of each component and the solubility in an organic solvent are required.
- Inorganic components can be dispersed by roll dispersion, but organic components are difficult to disperse by roll dispersion. Therefore, it is indispensable that the organic component is dissolved and dispersed in an organic solvent. If the organic component is not sufficiently dissolved, it may not be completely dissolved and may remain in the composition in the form of coarse particles. In particular, when the photopolymerization initiator contained in the solder resist ink does not dissolve sufficiently and remains in the composition in the form of coarse particles, the photocuring reaction becomes insufficient, and the original photocuring reaction is exhibited.
- organic solvents generally include petroleum aromatic solvents, glycol ethers, and glycol esters. Among them, an appropriate volatilization rate is considered in consideration of solubility in organic raw materials, workability, and storage stability. Organic solvents that have been used have been used. However, petroleum-based aromatic solvents, which have excellent solubility in organic raw materials, contain naphthalene, which is suspected of being a carcinogen, and have been demanded for countermeasures because of concern over adverse effects on the human body.
- the present invention provides an alkali development type photosensitive resin composition that is free of coarse particles, has excellent storage stability, suppresses deterioration of the working environment, and can form a pattern of a cured coating film with less harmful substances to the human body.
- the present inventors as an organic solvent that is responsible for dissolving and diluting a synthetic resin in an alkali development type photosensitive resin composition, are excellent in solubility and are suitable for the human body.
- the present inventors have found that the above-mentioned problems can be solved by using a specific organic solvent with less harmful substances.
- the present invention [1] Contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a compound having two or more ethylenically unsaturated groups in one molecule, and (D) a dibasic acid ester.
- An alkali development type photosensitive resin composition characterized by the above.
- the alkali development type photosensitive resin composition according to [1].
- the alkyls in (a), (b) and (c) are each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.
- the content of (D) dibasic acid ester is any one of [1] to [3], which is 1 to 60 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing resin.
- An alkali development type photosensitive resin composition is any one of [1] to [3], which is 1 to 60 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing resin.
- the alkali-developable photosensitive resin composition according to any one of [1] to [5] or the alkali-developable photosensitive resin composition is applied on a carrier film and dried.
- a printed wiring board comprising a cured product obtained by photocuring, or photocuring and heat curing, an obtained dry film. Is to provide.
- the alkali-developable photosensitive resin composition of the present invention uses a (D) dibasic acid ester having excellent solubility as an organic solvent, so that there are no coarse particles derived from organic components such as a photopolymerization initiator, and a cured coating film. It is possible to improve the characteristics of the cured film and to reduce the appearance defect of the cured coating film.
- the (D) dibasic acid ester of the present invention is particularly excellent in biodegradability, an alkali developing photosensitive resin composition having a low content of harmful substances that adversely affect the human body, the photosensitive resin composition Can be provided on a carrier film and dried, and a cured product of the photosensitive composition or the dry film, and a printed wiring board provided with the cured product can be provided. Furthermore, the alkali-developable photosensitive resin composition can suppress an increase in viscosity of the alkali-developable photosensitive resin composition by using (D) dibasic acid ester having an appropriate volatilization rate as an organic solvent. As a result, an alkali-developable photosensitive resin composition having excellent storage stability can be provided.
- the alkali-developable photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a compound having two or more ethylenically unsaturated groups in one molecule, and (D) It contains a dibasic acid ester.
- a photopolymerization initiator a compound having two or more ethylenically unsaturated groups in one molecule
- D It contains a dibasic acid ester.
- it has excellent solubility in organic components such as a photopolymerization initiator, so that it can form a cured coating film free of coarse particles, has good storage stability, and contains harmful substances that adversely affect the human body. A reduced amount of the composition is obtained.
- the alkali-developable photosensitive resin composition of the present invention is characterized by containing (D) a dibasic acid ester as an essential component, first, (D) the dibasic acid ester will be described.
- the ratio of each component constituting the (D) dibasic acid ester contained in the alkali development type photosensitive resin composition of the present invention is as follows: (a) 0 to 40% by mass of dialkyl adipate, (b) dialkyl glutarate 40 Particularly preferred are ⁇ 80 wt% and (c) 5-40 wt% dialkyl succinate. If this amount is deviated, the volatilization rate may be affected, and the following problems may be cited as defects of the alkali development type photosensitive resin composition.
- the alkyls in the components (a) to (c) are each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, preferably an alkyl group having 4 or less carbon atoms, Groups are more preferred.
- the alkyls in the components (a) to (c) may be the same in each component, or may be esters of different alkyls. Those having an alkyl group having 5 or more carbon atoms have slightly poor volatility, and the dryness to touch after drying becomes poor.
- examples of the alkyl group having 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, pentyl, and hexyl.
- examples of the cycloalkyl group having 5 to 8 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and dimethylcyclohexyl.
- the blending ratio of the (D) dibasic acid ester is suitably 1 to 60 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the following carboxyl group-containing resin (A).
- (D) If the amount of dibasic acid ester used is less than the above range, the solubility in organic components will be poor. On the other hand, if it is too much, the volatility will be slightly poor and the touch dryness after drying will be poor. It is not preferable.
- the proportion of (a) dialkyl adipate in (D) dibasic acid ester is 0 to 40% by mass, more preferably 5 to 30% by mass.
- A One dialkyl adipate may be used, or a mixture of two or more may be used.
- the ratio of (D) dialkyl glutarate to (D) dibasic acid ester is 40 to 80% by mass, more preferably 50 to 70% by mass.
- B Dialkyl glutarate may be used by 1 type, and 2 or more types of mixtures may be used for it.
- the ratio of (c) dialkyl succinate to (D) dibasic acid ester is 5 to 40% by mass, more preferably 10 to 30% by mass.
- C Dialkyl succinate may be used by 1 type, and 2 or more types of mixtures may be used for it.
- the (D) dibasic acid ester of the present invention is stored at a low temperature (5 ° C. or lower) because of its high dissolving power with respect to the components contained in the alkali-developable photosensitive resin composition, particularly the photopolymerization initiator. In this case, it is possible to prevent the occurrence of so-called reaggregation in which crystalline foreign matters are precipitated in the composition, and improve the storage stability of the alkali development type photosensitive resin composition.
- the organic solvent contained in the alkali-developable photosensitive resin composition of the present invention is safe for the global environment in order to further adjust the solubility and volatilization rate.
- a solvent having a propylene glycol skeleton, a solvent such as propionate, or a glycol ether or glycol ester solvent may be added as appropriate.
- Examples of the solvent having (di) propylene glycol skeleton include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and the like. I can do it.
- Examples of the propionic acid ester include methyl propionate, ethyl propionate, propyl propionate, methyl methoxypropionate, and ethyl methoxypropionate.
- examples of the solvent having a glycol ether or glycol ester skeleton include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether acetate.
- (D) dibasic acid ester or organic solvent other than the above (D) dibasic acid ester can be used when (A) carboxyl group-containing resin is produced, and this is separated after completion of the reaction. It can also be contained in the alkali-developable photosensitive resin composition of the present invention as it is.
- (A) Carboxyl group-containing resin Specific examples of the (A) carboxyl group-containing resin that can be suitably used in the alkali-developable photosensitive resin composition of the present invention include compounds listed below (oligomers and polymers). Any may be preferred).
- a carboxyl group-containing photosensitive resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
- a carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
- Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and another compound having an unsaturated double bond
- a photosensitive resin containing a hydroxyl group and a carboxyl group (7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group
- a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride (8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule.
- a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride is not limited to these.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- the acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g.
- the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
- the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary.
- the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
- the weight average molecular weight of the above (A) carboxyl group-containing resin varies depending on the resin skeleton, but generally it is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
- the weight average molecular weight is less than 2,000, the tack-free performance after application to the substrate and drying may be inferior, and the coating film after exposure is poor in moisture resistance, resulting in film loss during development, resolution. May be greatly inferior.
- the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
- Photopolymerization initiator (B) The photopolymerization initiator that can be suitably used in the alkali development type photosensitive resin composition of the present invention includes benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
- Benzoin and benzoin alkyl ethers acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1- [4- (4-benzoylphenylsulfanyl) Acetophenones such as -2-methyl-2- (4-methylphenylsulfanyl) propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl -2-dimethylamino-1- (4-morpholino Aminoacetophenones such as phenyl) -butanone-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-
- photopolymerization initiators may be used alone or in combination of two or more. Can be used.
- a preferred form of the photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, and commercially available products include Irgacure 907 manufactured by BASF Japan Ltd. Examples of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and commercially available products include Irgacure 369 manufactured by BASF Japan.
- the blending ratio of these (B) photopolymerization initiators is suitably 0.01 to 30 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. .
- the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition is deteriorated.On the other hand, when it is too much, a characteristic as a solder resist, for example, so-called halation called line thickening easily occurs, As a result, chemical resistance, solder heat resistance and the like are not preferable.
- (C) Compound having two or more ethylenically unsaturated groups in one molecule
- hydroxyalkyl acrylates such as 2-hydroxypropyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethyl Acrylamides such as acrylamide, N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Hexanediol and trimethylolpropane Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates such as imidazole adducts or propylene oxide adducts; phenoxy acrylates, bisphenol A diacrylates, and acryl
- 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
- the compounding amount of the compound (C) having two or more ethylenically unsaturated groups in one molecule is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Desirably, the ratio is more preferably 1 to 70 parts by mass.
- the blending amount is less than 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin, the photocurability of the resulting alkali-developable photosensitive resin composition is lowered, and the alkali after irradiation with active energy rays Development is not preferable because pattern formation becomes difficult.
- the amount exceeds 100 parts by mass the solubility in an aqueous alkali solution is reduced and the coating film becomes brittle, which is not preferable.
- Thermosetting component The alkali-developable photosensitive resin composition used in the present invention has two or more reactive groups (cyclic ether group and cyclic thioether group (E) in the molecule in order to impart heat resistance.
- cyclic ether group and cyclic thioether group (E) in the molecule in order to impart heat resistance.
- the (E) thermosetting component is a compound having two or more of either one of the three, four or five-membered cyclic ether group or the cyclic thioether group in the molecule, for example, (E -1) a compound having at least two epoxy groups in the molecule, ie, a polyfunctional epoxy compound, (E-2) a compound having at least two oxetanyl groups in the molecule, ie, a polyfunctional oxetane compound, (E -3) A compound having two or more cyclic thioether groups in the molecule, that is, an episulfide resin.
- Examples of the (E-1) polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 1505, and Epotot manufactured by Tohto Kasei Co., Ltd. YD-011, YD-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.
- A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (both trade names); jER152, jER165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 542, Sumitomo Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N.
- Type or biphenol type epoxy resin or a mixture thereof Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); Tetraphenylol ethane type epoxy resin such as Epicoat YL-931 (all trade name) manufactured by Mitsubishi Chemical; TEPIC etc.
- Examples of the (E-2) polyfunctional oxetane compound 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- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) 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-
- Examples of the compound having two or more cyclic thioether groups in the (E-3) molecule include bisphenol A type episulfide resin YL7000 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 two or more cyclic (thio) ether groups in the molecule is preferably a cyclic (thio) ether group with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. Is in the range of 0.6 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents.
- the amount exceeds 2.0 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
- thermosetting component having two or more cyclic (thio) ether groups in the molecule (E) it is preferable to contain a thermosetting catalyst.
- 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, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all dimethylamine block isocyanate compounds manufactured by San Apro) Product names), DBU, DBN, U
- the present invention is not limited to these, as long as it is a thermosetting catalyst for an epoxy resin or an oxetane compound, or any one that promotes the reaction of at least one of an epoxy group and an oxetanyl group with a carboxyl group, either alone or in two types A mixture of the above may be used.
- the alkali-developable photosensitive resin composition of the present invention may further comprise barium sulfate, barium titanate, silicon oxide powder, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, water as necessary.
- Known inorganic or organic fillers such as aluminum oxide, glass fiber, carbon fiber, mica powder, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.
- known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc.
- known conventional methods such as fine silica, organic bentonite, montmorillonite, etc.
- a defoamer and leveling agent such as a thickener, silicone, fluorine, and polymer
- an adhesion-imparting agent such as an imidazole, thiazole, and triazole
- silane coupling agent such as an imidazole, thiazole, and triazole
- known additives such as phosphorus-based and sulfur-based antioxidants, hindered amine light stabilizers, and the like can be blended.
- the dry film of the present invention is obtained by coating and drying the alkali-developable photosensitive resin composition of the present invention on a film (carrier film).
- the alkali development type photosensitive resin composition of the present invention is diluted with the above organic solvent to an appropriate viscosity, followed by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater.
- a film can be obtained by applying a uniform thickness on a support with a 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 10 to 150 ⁇ m, preferably 20 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 peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the 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 support is more than What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
- the alkali-developable photosensitive resin composition of the present invention When used for forming a solder resist on a printed wiring board, it is adjusted to a viscosity suitable for the coating method as necessary, and then this is used, for example, for a printed wiring in which a circuit is formed in advance.
- a tack-free coating film is formed by applying a screen printing method, curtain coating method, spray coating method, roll coating method, etc. to a plate and drying it at a temperature of about 60 to 100 ° C. if necessary. it can.
- the dry film it is bonded onto a substrate using a hot roll laminator or the like (bonded so that the photosensitive resin composition layer and the substrate are in contact with each other).
- a dry film having a peelable cover film on the photosensitive resin composition layer of the film after the cover film is peeled off, the photosensitive resin composition layer and the substrate are hot so that they come into contact with each other. Bond using a roll laminator.
- the resist pattern can be formed by selectively exposing with an actinic ray through a photomask having a predetermined exposure pattern, and developing the unexposed portion with an alkaline aqueous solution. Further, for example, 300 to 500 mJ / cm 2 UV irradiation is performed. Polymerization of the photosensitive resin component is promoted in addition to the curing reaction of the thermosetting component by photocuring or heating to a temperature of about 140 to 180 ° C., and the resulting resist film has heat resistance. Various properties such as property, solvent resistance, acid resistance, moisture absorption resistance, PCT resistance, adhesion, and electrical characteristics can be improved.
- alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
- a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a semiconductor laser, a solid laser, a xenon lamp, a metal halide lamp, or the like is appropriate.
- the photopolymerizable resin composition of the present invention and the curable film formed of a dry film are suitable as a permanent film of a printed wiring board, and particularly suitable as a solder resist or an interlayer insulating material.
- This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours.
- the obtained reaction product was cooled to 80 to 90 ° C., 91.2 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled and taken out.
- the carboxyl group-containing photopolymerizable unsaturated compound thus obtained had a non-volatile content of 65% and a solid acid value of 87.5 mgKOH / g.
- this reaction product solution is referred to as A varnish.
- reaction product solution was referred to as B varnish.
- reaction product was cooled to 80 to 90 ° C., 91.2 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled and taken out.
- the carboxyl group-containing photopolymerizable unsaturated compound thus obtained had a non-volatile content of 65% and a solid acid value of 87.5 mgKOH / g.
- this reaction product solution is referred to as C varnish.
- Performance evaluation (1) Touch-drying property after temporary drying Each surface of the alkali-developable photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 is screen-printed on a copper-clad laminate that has been buffed. The board
- Viscosity evaluation 50 g of each of the alkali development type photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 is weighed, and 50 ° C. After leaving it to stand for 5 days, the viscosity was measured using an E-type viscometer, and the viscosity difference (thickening rate) from before leaving at 50 ° C. was evaluated.
- Table 2 shows the results of the above tests.
- Example 1 to 5 using a dibasic acid ester as a solvent are compared with the comparative examples in dryness to touch, re-aggregation test, and viscosity evaluation. It can be seen that all the characteristics of the appearance evaluation are good. Moreover, it turns out that Example 1, Example 2, and Example 3 which all contain the dibasic acid ester and the use solvent and dilution solvent to a varnish are especially favorable.
- Comparative Example 1 using carbitol acetate and a petroleum aromatic solvent as a solvent for varnish and dipropylene glycol monomethyl ether as a diluting solvent is a naphthalene of which concern is harmful to human body in a petroleum aromatic solvent. It was also found that the viscosity evaluation result was poor and the storage stability was poor. Further, Comparative Example 2 using carbitol acetate and dipropylene glycol monomethyl ether as a solvent for varnish and carbitol acetate as a diluent solvent has poor viscosity evaluation and re-agglomeration test results, inferior storage stability, and coating film surface It was found that there were many grains above and the result of appearance evaluation was bad.
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Abstract
Description
[1](A)カルボキシル基含有樹脂、(B)光重合開始剤、(C)1分子中に2個以上のエチレン性不飽和基を有する化合物、および(D)二塩基酸エステルを含有することを特徴とするアルカリ現像型感光性樹脂組成物。
[2](D)二塩基酸エステルが、(a)アジピン酸ジアルキル0~40質量%、(b)グルタル酸ジアルキル40~80質量%、および(c)コハク酸ジアルキル5~40質量%の混合物である[1]に記載のアルカリ現像型感光性樹脂組成物。
ここで(a)、(b)、(c)のアルキルは、それぞれ独立して、炭素数1~6のアルキル基または炭素数5~8のシクロアルキル基である。
[3](D)二塩基酸エステルが、アジピン酸ジメチル、グルタル酸ジメチル、およびコハク酸ジメチルの混合物である[1]または[2]に記載のアルカリ現像型感光性樹脂組成物。
[4](D)二塩基酸エステルの含有量が、(A)カルボキシル基含有樹脂100質量部に対して、1~60質量部である[1]乃至[3]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物。
[5]さらに、(E)熱硬化性成分を含有することを特徴とする[1]乃至[4]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物。
[6]基材上に塗布して用いられる[1]乃至[5]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物。
[7][1]乃至[5]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルム。
[8][1]乃至[5]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物、または、該アルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルムを、基材上にて光硬化、または、光硬化および熱硬化して得られることを特徴とする硬化物。
[9]前記[1]乃至[5]のいずれか1項に記載のアルカリ現像型感光性樹脂組成物、または、該アルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルムを光硬化、または光硬化および熱硬化して得られる硬化物を備えることを特徴とするプリント配線板。
を提供するものである。
また、本発明の(D)二塩基酸エステルは、特に生分解性に優れることから、人体へ悪影響を及ぼす有害物質の含有量が低いアルカリ現像型感光性樹脂組成物、該感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルム、該感光性組成物または該ドライフィルムの硬化物、ならびに該硬化物を備えるプリント配線板を提供することができる。
さらに、アルカリ現像型感光性樹脂組成物は、有機溶剤として適度な揮発速度を有する(D)二塩基酸エステルを使用することにより、アルカリ現像型感光性樹脂組成物の粘度上昇を抑える事ができ、結果、貯蔵安定性に優れるアルカリ現像型感光性樹脂組成物を提供することができる。
すなわち、各上限値を超えると揮発速度が遅くなり、アルカリ現像型感光性樹脂組成物内に(D)二塩基酸エステルが多量に残留し、所謂、ベタツキと言われる指触乾燥性が悪くなる。
一方、各下限値未満であると揮発速度が速くなり、アルカリ現像型感光性樹脂組成物の粘度が上昇し、貯蔵安定性が悪くなる。
(a)~(c)成分のアルキルは、各成分において同一であってもよく、異なるアルキルのエステルであってもよい。
炭素数5以上のアルキル基のものは、揮発性がやや乏しく、乾燥後の指触乾燥性が悪くなる。
上記(D)二塩基酸エステルの配合割合は、下記カルボキシル基含有樹脂(A)100質量部に対して、1~60質量部が適当であり、好ましくは5~40質量部である。(D)二塩基酸エステルの使用量が上記範囲より少ない場合、有機成分に対する溶解性が悪くなり、一方、多過ぎる場合は、揮発性がやや乏しく、乾燥後の指触乾燥性が悪くなるので好ましくない。
(D)二塩基酸エステルに占める(c)コハク酸ジアルキルの比率は、5~40質量%であり、より好ましくは10~30質量%である。(c)コハク酸ジアルキルは、1種で用いてもよく、2種以上の混合物を用いてもよい。
本発明のアルカリ現像型感光性樹脂組成物に好適に用いることができる(A)カルボキシル基含有樹脂の具体例としては、以下に列挙するような化合物(オリゴマーおよびポリマーのいずれかでよい)が好ましい。
(1)(メタ)アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の1種類以上とを共重合することにより得られるカルボキシル基含有感光性樹脂、
(2)(メタ)アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の1種類以上との共重合体に、グリシジル(メタ)アクリレートや3,4-エポキシシクロヘキシルメチル(メタ)アクリレートなどのエポキシ基と不飽和二重結合を有する化合物や(メタ)アクリル酸クロライドなどによって、エチレン性不飽和基をペンダントとして付加させることによって得られるカルボキシル基含有感光性樹脂、
(3)グリシジル(メタ)アクリレートや3,4-エポキシシクロヘキシルメチル(メタ)アクリレート等のエポキシ基と不飽和二重結合を有する化合物と、それ以外の不飽和二重結合を有する化合物との共重合体に、(メタ)アクリル酸などの不飽和カルボン酸を反応させ、生成した二級の水酸基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、
(4)無水マレイン酸などの不飽和二重結合を有する酸無水物と、それ以外の不飽和二重結合を有する化合物との共重合体に、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基と不飽和二重結合を有する化合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)多官能エポキシ化合物と不飽和モノカルボン酸を反応させ、生成した水酸基に飽和または不飽和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)ポリビニルアルコール誘導体などの水酸基含有ポリマーに、飽和または不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に一分子中にエポキシ基と不飽和二重結合を有する化合物を反応させて得られる水酸基およびカルボキシル基を含有する感光性樹脂、
(7)多官能エポキシ化合物と、不飽和モノカルボン酸と、一分子中に少なくとも1個のアルコール性水酸基と、エポキシ基と反応するアルコール性水酸基以外の1個の反応性基を有する化合物との反応生成物に、飽和または不飽和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、
(8)一分子中に少なくとも2個のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン樹脂中の第一級水酸基に対して飽和または不飽和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、および、
(9)多官能エポキシ樹脂に不飽和モノカルボン酸を反応させた後、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樹脂に、さらに、分子中に1個のオキシラン環と1個以上のエチレン性不飽和基を有する化合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、
(10)2官能エポキシ化合物と不飽和モノカルボン酸を反応させ、生成した水酸基に飽和または不飽和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、
などが挙げられるが、これらに限定されるものではない。
これらの例示の中でも好ましいものとしては、上記(2)、(5)、(7)、(9)のカルボキシル基含有樹脂である。
なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語であり、他の類似の表現についても同様である。
また、上記(A)カルボキシル基含有樹脂の酸価は、40~200mgKOH/gの範囲が望ましく、より好ましくは45~120mgKOH/gの範囲である。カルボキシル基含有樹脂の酸価が40mgKOH/g未満であるとアルカリ現像が困難となり、一方、200mgKOH/gを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。
本発明のアルカリ現像型感光性樹脂組成物に好適に用いることができる(B)光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-[4-(4-ベンゾイルフェニルスルファニル)-2-メチル-2-(4-メチルフェニルスルファニル)プロパン-1-オン等のアセトフェノン類;2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパノン-1、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1等のアミノアセトフェノン類;2-メチルアントラキノン、2-エチルアントラキノン、2-ターシャリーブチルアントラキノン、1-クロロアントラキノン等のアントラキノン類;2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾフェノン等のベンゾフェノン類またはキサントン類;ビス(2,6‐ジメトキシベンゾイル)(2,4,4‐トリメチルペンチル)ホスフィンオキシド、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド、エチル-2,4,6-トリメチルベンゾイルフェニルホスフィネイト等のアシルホスフィンオキサイド類;各種パーオキサイド類などが挙げられ、これら公知慣用の光重合開始剤を単独でまたは2種以上を組み合わせて用いることができる。
(B)光重合開始剤の好ましい形態としては、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパノン-1、市販品としては、BASFジャパン社製のイルガキュアー907と2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、市販品としては、BASFジャパン社製のイルガキュアー369などが挙げられる。
本発明のアルカリ現像型感光性樹脂組成物に用いられる(C)1分子中に2個以上のエチレン性不飽和基を有する化合物は、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しまたは不溶化を助けるものである。このような化合物の具体例としては、2-ヒドロキシプロピルアクリレート等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等のグリコールのモノまたはジアクリレート類;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等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等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等の多価アルコールまたはこれらのエチレンオキサイド付加物もしくはプロピレンオキサイド付加物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物もしくはプロピレンオキサイド付加物などのアクリレート類;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等のグリシジルエーテルのアクリレート類;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種などが挙げられる。
さらに、クレゾールノボラック型エポキシ樹脂等の多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレート等のヒドロキシアクリレートとイソホロンジイソシアネート等のジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物などが挙げられる。
本発明に用いるアルカリ現像型感光性樹脂組成物は、耐熱性を付与するために、(E)分子中に2個以上の反応基(環状エーテル基および環状チオエーテル基(以下、環状(チオ)エーテル基の少なくとも何れか一方と略す))を有する熱硬化性成分を配合することが好ましい。
本発明のアルカリ現像型感光性樹脂組成物は、さらに必要に応じて、硫酸バリウム、チタン酸バリウム、酸化ケイ素粉、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、ガラス繊維、炭素繊維、雲母粉などの公知慣用の無機または有機フィラー、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、t-ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤およびレベリング剤の少なくとも何れか1種、イミダゾール系、チアゾール系、トリアゾール系等の密着性付与剤やシランカップリング剤、フェノール系、リン系、イオウ系等の酸化防止剤、ヒンダードアミン系光安定剤等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。
ドライフィルム化に際しては、本発明のアルカリ現像型感光性樹脂組成物を適切な粘度に上記有機溶剤で希釈し、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支持体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、10~150μm、好ましくは20~60μmの範囲で適宜選択される。
上記現像に使用されるアルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。また、光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、半導体レーザー、固体レーザー、キセノンランプまたはメタルハライドランプなどが適当である。
クレゾールノボラック型エポキシ樹脂のEPICLON N-695(DIC社製、エポキシ当量=214)214部を撹拌機および還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート103部、二塩基酸エステル溶剤(デュポン製 商品名:DBE[アジピン酸ジメチル;10-25%、グルタル酸ジメチル;55-65%、コハク酸ジメチル;15-25%])103部を加えて加熱溶解した。次に、重合禁止剤としてハイドロキノン0.1部と、反応触媒としてトリフェニルホスフィン2.0部を加えた。この混合物を95~105℃に加熱し、アクリル酸72部を徐々に滴下し、16時間反応させた。得られた反応生成物を80~90℃まで冷却し、テトラヒドロフタル酸無水物91.2部を加えて8時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有光重合性不飽和化合物は、不揮発分65%、固形物の酸価87.5mgKOH/gであった。以下、この反応生成物の溶液をAワニスと称す。
クレゾールノボラック型エポキシ樹脂のEPICLON N-695(DIC社製、エポキシ当量=214)214部を撹拌機および還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート103部、石油系芳香族溶剤(出光興産製、商品名:イプゾール150)103部を加えて加熱溶解した。次に、重合禁止剤としてハイドロキノン0.1部と、反応触媒としてトリフェニルホスフィン2.0部を加えた。この混合物を95~105℃に加熱し、アクリル酸72部を徐々に滴下し、16時間反応させた。得られた反応生成物を80~90℃まで冷却し、テトラヒドロフタル酸無水物91.2部を加えて8時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有光重合性不飽和化合物は、不揮発分65%、固形物の酸価87.5mgKOH/gであった。以下、この反応生成物の溶液をBワニスと称す。
クレゾールノボラック型エポキシ樹脂のEPICLON N-695(DIC社製、エポキシ当量=214)214部を撹拌機および還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート103部、ジプロピレングリコールモノメチルエーテル(東邦化学工業製、商品名:ハイソルブ DPM)103部を加えて加熱溶解した。次に、重合禁止剤としてハイドロキノン0.1部と、反応触媒としてトリフェニルホスフィン2.0部を加えた。この混合物を95~105℃に加熱し、アクリル酸72部を徐々に滴下し、16時間反応させた。得られた反応生成物を80~90℃まで冷却し、テトラヒドロフタル酸無水物91.2部を加えて8時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有光重合性不飽和化合物は、不揮発分65%、固形物の酸価87.5mgKOH/gであった。以下、この反応生成物の溶液をCワニスと称す。
(1)仮乾燥後の指触乾燥性
上記の実施例1~5および比較例1~2の各アルカリ現像型感光性樹脂組成物を、バフロール研磨された銅張り積層板にスクリーン印刷にて全面塗布し、80℃で30分間、乾燥させた基板を作製し、その塗膜表面の指触乾燥性を評価した。
○:まったくベタつきがないもの
△:僅かにベタつきのあるもの
×:ベタつきのあるもの
(2)再凝集試験
上記の実施例1~5および比較例1~2の各アルカリ現像型感光性樹脂組成物を、50g秤取り、50℃下に1日放置した後、4℃下1日更に放置した後の組成物中に結晶物が存在するかを評価した。
○:まったく結晶物が存在しない
×:結晶物が存在する
(3)粘度評価
上記の実施例1~5および比較例1~2の各アルカリ現像型感光性樹脂組成物を50g秤取り、50℃下に5日放置した後、E型粘度計を用いて粘度を測定し、50℃放置前との粘度差(増粘率)を評価した。
○:増粘率25%以下
△:増粘率26%以上、40%以下
×:増粘率41%以上
(4)外観評価
上記の実施例1~5および比較例1~2の各アルカリ現像型感光性樹脂組成物を、バフロール研磨された銅張り積層板(塗布面積:105cm2)にスクリーン印刷にて全面塗布し、80℃で30分間、乾燥させた基板を作製し、その塗膜表面上の粒の有無を目視にて評価した。乾燥後膜厚は15μm±2μm。
○:粒個数が、0個
△:粒個数が、5個以下
×:粒個数が、6個以上
(5)はんだ耐熱性
上記の実施例1~5および比較例1~2の各アルカリ現像型感光性樹脂組成物を光硬化と熱硬化させた塗膜をJIS C6481の試験方法に従いロジン系および水溶性フラックスを用いて260℃のはんだ浴に10秒2回浸漬し、塗膜の状態を確認した。評価基準は以下の通りである。
○:塗膜に剥がれ等異常のないこと
△:塗膜に軽微の剥がれのあるもの
×:塗膜に膨れ、剥がれのあるもの
一方、ワニスへの使用溶剤としてカルビトールアセテートおよび石油系芳香族溶剤、希釈溶剤としてジプロピレングリコールモノメチルエーテルを用いる比較例1は石油系芳香族溶剤の中に人体への有害性が懸念されるナフタレンを含有し、また粘度評価結果が悪く、貯蔵安定性に劣ることが分かった。
また、ワニスへの使用溶剤としてカルビトールアセテートおよびジプロピレングリコールモノメチルエーテル、希釈溶剤としてカルビトールアセテートを用いる比較例2は粘度評価および再凝集試験結果が悪く、貯蔵安定性に劣り、また塗膜表面上の粒も多く、外観評価結果も悪いことが分かった。
Claims (9)
- (A)カルボキシル基含有樹脂、(B)光重合開始剤、(C)1分子中に2個以上のエチレン性不飽和基を有する化合物、および(D)二塩基酸エステルを含有することを特徴とするアルカリ現像型感光性樹脂組成物。
- (D)二塩基酸エステルが、(a)アジピン酸ジアルキル0~40質量%、(b)グルタル酸ジアルキル40~80質量%、および(c)コハク酸ジアルキル5~40質量%の混合物である請求項1記載のアルカリ現像型感光性樹脂組成物。
ここで(a)、(b)、(c)のアルキルは、それぞれ独立して、炭素数1~6のアルキル基または炭素数5~8のシクロアルキル基である。 - (D)二塩基酸エステルが、アジピン酸ジメチル、グルタル酸ジメチル、およびコハク酸ジメチルの混合物である請求項1記載のアルカリ現像型感光性樹脂組成物。
- (D)二塩基酸エステルの含有量が、(A)カルボキシル基含有樹脂100質量部に対して、1~60質量部である請求項1記載のアルカリ現像型感光性樹脂組成物。
- さらに、(E)熱硬化性成分を含有することを特徴とする請求項1記載のアルカリ現像型感光性樹脂組成物。
- 基材上に塗布して用いられる請求項1記載のアルカリ現像型感光性樹脂組成物。
- 請求項1乃至5のいずれか1項記載のアルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルム。
- 請求項1乃至5のいずれか1項記載のアルカリ現像型感光性樹脂組成物、または、該アルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルムを、基材上にて光硬化、または、光硬化および熱硬化して得られることを特徴とする硬化物。
- 前記請求項1乃至5のいずれか1項記載のアルカリ現像型感光性樹脂組成物、または、該アルカリ現像型感光性樹脂組成物を、キャリアフィルム上に塗布、乾燥して得られるドライフィルムを光硬化、または光硬化および熱硬化して得られる硬化物を備えることを特徴とするプリント配線板。
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JP2014522355A JP5952904B2 (ja) | 2012-06-29 | 2012-08-15 | アルカリ現像型感光性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 |
US14/394,179 US20150079505A1 (en) | 2012-06-29 | 2012-08-15 | Alkaline-developable photosensitive resin composition, dry film, cured article, and printed wiring board |
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WO2023190454A1 (ja) * | 2022-03-29 | 2023-10-05 | 太陽ホールディングス株式会社 | 感光性樹脂組成物およびプリント配線板の製造方法 |
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JP6026347B2 (ja) * | 2013-04-23 | 2016-11-16 | 日東電工株式会社 | 感光性エポキシ樹脂組成物および光導波路コア層形成用硬化性フィルム、ならびにそれを用いた光導波路、光・電気伝送用混載フレキシブルプリント配線板 |
JP5882510B2 (ja) * | 2014-06-30 | 2016-03-09 | 太陽インキ製造株式会社 | 感光性ドライフィルムおよびそれを用いたプリント配線板の製造方法 |
JP6578295B2 (ja) * | 2014-10-16 | 2019-09-18 | 太陽インキ製造株式会社 | 積層構造体、ドライフィルムおよびフレキシブルプリント配線板 |
KR20160115718A (ko) * | 2015-03-25 | 2016-10-06 | 세키스이가가쿠 고교가부시키가이샤 | 2액 혼합형의 제1, 제2 액 및 프린트 배선판의 제조 방법 |
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KR20140121862A (ko) | 2014-10-16 |
JP5952904B2 (ja) | 2016-07-13 |
TWI537680B (zh) | 2016-06-11 |
CN107422604A (zh) | 2017-12-01 |
JPWO2014002294A1 (ja) | 2016-05-30 |
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MY171600A (en) | 2019-10-21 |
US20150079505A1 (en) | 2015-03-19 |
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