WO2013047305A1 - 感光性樹脂組成物及びドライフィルムレジスト - Google Patents
感光性樹脂組成物及びドライフィルムレジスト Download PDFInfo
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- WO2013047305A1 WO2013047305A1 PCT/JP2012/073999 JP2012073999W WO2013047305A1 WO 2013047305 A1 WO2013047305 A1 WO 2013047305A1 JP 2012073999 W JP2012073999 W JP 2012073999W WO 2013047305 A1 WO2013047305 A1 WO 2013047305A1
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- photosensitive 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
- G03F7/038—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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
Definitions
- the present invention relates to a photosensitive resin composition excellent in high sensitivity, high insulation, dielectric properties, heat resistance, etc., and a dry film resist using the photosensitive resin composition.
- an insulating resin material used for a printed wiring board is also required to have heat resistance, fine workability, electrical characteristics, and the like.
- a method of patterning by exposure and development is known, and a photosensitive resin composition has been used there, but high sensitivity, adhesion to the substrate, electrical characteristics, Many characteristics such as plating resistance, heat resistance, and dimensional stability have been demanded.
- the electrical characteristics have the disadvantage that the dielectric characteristics in the high frequency region are poor, and cannot be used as a material for a multilayer printed wiring board on which a high frequency circuit is mounted.
- the photosensitive resin composition used in these fields generally contains a polymerizable oligomer having an unsaturated double bond, a polymerizable monomer, and a photopolymerization initiator as essential components.
- the polymerizable oligomer mainly used as the photosensitive component include polyester acrylate, urethane acrylate, and epoxy acrylate. These polymerizable oligomers have a polymerizable unsaturated group, and thus are photopolymerization initiators. It reacts with other polymerizable monomers with radicals caused by, and becomes a cured product by crosslinking.
- These polymerizable compounds generally have a small molecular weight and are cured instantaneously by light irradiation. Therefore, there is a problem in that residual stress is generated in the coating film and adhesion to a substrate and mechanical properties are deteriorated.
- high molecular weight polymerizable compounds have been studied, but a large amount of solvent and reactive diluent are required to adjust the viscosity so that it can be applied.
- Such a photosensitive resin composition has poor mechanical strength and chemical resistance. Further, there is a problem that the solubility in an alkali developer is lowered due to the high molecular weight, and development is impossible.
- Patent Document 1 attempts to improve dielectric properties by using an alkali-developable photosensitive polyfunctional vinyl compound.
- Patent Documents 2 and 3 disclose solvent-soluble polyfunctional vinyl copolymers, but they did not have alkali developability.
- the object of the present invention is a pattern that can be developed with an alkaline aqueous solution, has high sensitivity, and has excellent dielectric properties that have been difficult to realize simultaneously with these properties, as well as various properties such as insulation and heat resistance. It is providing the photosensitive resin composition and dry film resist which can form a thin film easily.
- the present invention relates to a copolymer obtained by copolymerizing component (A): divinyl compound (a) 20 to 99 mol% and monovinyl compound (b) 80 to 1 mol%, A solvent-soluble polyfunctional vinyl copolymer in which the content of the structural unit containing an unreacted vinyl group represented by the following formula (a1) is 10 to 90 mol%, (B) component: an alkali-soluble resin component containing a carboxyl group-containing copolymer (b) obtained by reacting a polyol compound and a polyvalent carboxylic acid, and having an acid value of 50 to 200 mg KOH / g, and (C) Component: A photosensitive resin composition containing a photoinitiator, wherein the blending amount of the component (A) with respect to the total of the components (A), (B) and (C) is 1 to 98.9 wt%, (B The present invention relates to a photosensitive resin composition capable of alkali development, wherein the blending amount
- R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.
- the above is a solvent-soluble polyfunctional vinyl copolymer having a phenolic hydroxyl group at the terminal and the introduction amount is 2.2 / molecule or more, or the solvent-soluble polyfunctional vinyl copolymer is represented by the following formula ( It preferably has a terminal group containing an unsaturated bond represented by a2).
- R 2 is a hydrocarbon group having 1 to 18 carbon atoms which may contain an etheric oxygen atom or a thioetheric sulfur atom, and R 3 is hydrogen or a methyl group.
- the weight average molecular weight of the carboxyl group-containing copolymer (b) is preferably 3,000 to 40,000.
- the present invention provides a dry film resist in which a photosensitive resin layer is provided on a support substrate that can be peeled, wherein the photosensitive resin layer is composed of the photosensitive resin composition described above. It relates to a film resist.
- the photosensitive resin composition of the present invention can be developed with a solvent-soluble polyfunctional vinyl copolymer (hereinafter also referred to as component (A) or polyfunctional vinyl copolymer) and an alkaline aqueous solution as component (B).
- component (A) or polyfunctional vinyl copolymer a solvent-soluble polyfunctional vinyl copolymer
- component (B) an alkaline aqueous solution
- the main component of the alkali-soluble resin component means 50 wt% or more, preferably 80 wt% or more.
- the alkali-soluble resin component is not particularly limited as long as it contains a component that gives a resin that can be developed with an aqueous alkali solution after exposure. It is preferable to contain a component that becomes a resin.
- the resin or resin-forming component excluding the polyfunctional vinyl copolymer in the photosensitive resin composition may be simply referred to as an alkali-soluble resin.
- the blending amount of the component (A) is 1 to 98.9 wt% and the blending amount of the component (B) is 98.9 to 1 wt% with respect to the sum of the components (A), (B) and (C). .
- the blending amount of the component (A) is preferably 1 to 50 wt%, more preferably 5 to 24 wt%. If the blending amount of the component (A) is small, the effect on the low dielectric property and moisture resistance is lowered. Too much is not preferable because developability deteriorates.
- the polyfunctional vinyl copolymer of component (A) is known and can be selected and used. For example, it can be obtained according to the methods disclosed in JP-A No. 2004-123873, JP-A No. 2005-213443, WO 2009/110453, and the like. Specifically, a divinyl compound and at least one monovinyl compound are used for copolymerization to obtain a copolymer having a reactive pendant vinyl group represented by the formula (a1). Furthermore, as described in the above-mentioned patent document, those having other terminal groups other than vinyl groups introduced at the terminals can also be used, particularly for compounds having an unsaturated bond in the molecule such as phenoxy methacrylates.
- divinyl compound used here examples include divinyl aromatic compounds typified by divinylbenzene, aliphatics typified by ethylene glycol di (meth) acrylate, and alicyclic (meth) acrylates.
- the monovinyl compound used here may be any compound having an olefinic double bond copolymerizable with styrene, such as aromatic vinyl monomers such as paramethylstyrene, acrylic acid such as acrylic acid and methacrylic acid. Acid monomers, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic monomers such as butyl acrylate and methyl methacrylate, ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid, phenylmaleimide, cyclohexyl Examples thereof include imide monomers such as maleimide.
- a method for producing a polyfunctional vinyl copolymer for example, two or more kinds of compounds selected from divinyl aromatic compounds, monovinyl aromatic compounds and other monovinyl compounds are used as promoters selected from Lewis acid catalysts and ester compounds. It can be obtained by cationic copolymerization in the presence. Further, when a (meth) acrylate divinyl or monovinyl compound is used, the reaction does not proceed in cationic polymerization, and therefore, it can be obtained by radical polymerization in the presence of a radical catalyst such as peroxide.
- a radical catalyst such as peroxide.
- the amount of divinyl compound and monovinyl compound used is determined so as to give the composition of the polyfunctional vinyl copolymer used in the present invention, but the divinyl compound is 20 to 99 mol%, preferably 20 to 50 mol%, more preferably 30 to 50 mol% is used.
- the monovinyl compound is used in an amount of 80 to 1 mol%, preferably 80 to 50 mol%, more preferably 70 to 50 mol% of all monomers.
- cationic polymerization such as 2-phenoxyethyl methacrylate, those acting as terminal modifiers are not calculated as monomers.
- the Lewis acid catalyst used in the production of the polyfunctional vinyl copolymer is not particularly limited as long as it is a compound composed of a metal ion (acid) and a ligand (base) and can receive an electron pair. Can be used. From the viewpoints of control of molecular weight and molecular weight distribution and polymerization activity, boron trifluoride ether (diethyl ether, dimethyl ether, etc.) complexes are most preferably used.
- the Lewis acid catalyst is used in the range of 0.001 to 10 mol, more preferably 0.001 to 0.01 mol, relative to 1 mol of the monomer compound. An excessive amount of the Lewis acid catalyst is not preferable because the polymerization rate becomes too high and it becomes difficult to control the molecular weight distribution.
- the cocatalyst includes one or more selected from ester compounds.
- ester compounds having 4 to 30 carbon atoms are preferably used from the viewpoint of controlling the polymerization rate and the molecular weight distribution of the copolymer.
- ethyl acetate, propyl acetate and butyl acetate are preferably used.
- the cocatalyst is used in the range of 0.001 to 10 mol, more preferably 0.01 to 1 mol, relative to 1 mol of the monomer compound.
- the amount of the cocatalyst used is excessive, the polymerization rate decreases and the yield of the copolymer decreases.
- the amount of the cocatalyst used is too small, the selectivity of the polymerization reaction is lowered, the molecular weight distribution is increased, the gel is generated, and the polymerization reaction is difficult to control.
- a catalyst used for producing a polyfunctional vinyl copolymer by radical polymerization monofunctional compounds such as azo compounds represented by azobisisobutyronitrile, dibenzoyl peroxide, t-butylperoxybenzoate, etc.
- Bifunctional or higher functional peroxides such as functional peroxides and 1,1-bis (t-butylperoxy) cyclohexane, are exemplified, and may be used alone or in combination of two or more. Can do.
- the polyfunctional vinyl copolymer used in the present invention can be obtained by the above production method, but it is necessary to leave a part of the vinyl group of the divinyl compound used as a monomer without polymerizing. . Then, on average, 2 or more, preferably 3 or more vinyl groups are present in one molecule.
- This vinyl group exists mainly as a structural unit represented by the above formula (a1). Then, by leaving a part of the vinyl group without being polymerized, the crosslinking reaction can be suppressed and solvent solubility can be imparted.
- solvent-soluble means that it is soluble in toluene, xylene, THF, dichloroethane, or chloroform.
- the weight average molecular weight (Mw) of the polyfunctional vinyl copolymer is preferably 1,000 to 100,000, more preferably 5,000 to 70,000. If it is smaller than 1000, the viscosity when the photosensitive resin composition is made becomes low, it becomes difficult to form a thick film when coated, and tackiness occurs when it is made a dry film. descend. Moreover, when Mw is 100,000 or more, the solubility when it is used as a composition is reduced, appearance defects are generated, and alkali solubility is lowered due to high molecular weight, so that developability tends to deteriorate. .
- the polyfunctional vinyl copolymer preferably has a phenolic hydroxyl group derived from the polymerization additive or a structural unit represented by the above formula (2) at a part of its terminal.
- the amount introduced at the end is preferably 2.2 / molecule or more.
- a resin composition having improved development characteristics with an alkaline solution can be obtained.
- the polyfunctional vinyl copolymer is calculated, It is not calculated as a soluble resin.
- R 2 and R 3 have the above meaning, and R 2 is preferably an alkylene group having 1 to 6 carbon atoms.
- the unit containing a vinyl group derived from a divinyl compound introduced into the polyfunctional vinyl copolymer has a structural unit represented by the above formula (a1), and the molar fraction of the structural unit (a1) is 0.1. Is preferably from 0.9 to 0.9, preferably from 0.1 to 0.5, and more preferably from 0.1 to 0.3.
- the molar fraction is less than 0.1, the crosslinking density of the cured product is lowered, and the water resistance, migration resistance, and heat resistance are lowered, which is not preferable.
- it exceeds 0.9 excessive curing of the cured product proceeds and becomes brittle, which is not preferable.
- those obtained by terminal modification with a compound having an unsaturated bond in the molecule include, in addition to the structural unit represented by the formula (a1), the terminal unsaturated bond-containing structural unit (a2) is also a vinyl group. Therefore, the total molar fraction (a3) of both is preferably 0.1 to 0.9, preferably 0.1 to 0.5, more preferably 0.1 to 0.3. is there.
- the terminal unsaturated bond-containing structural unit (a2) is excellent in photoreactivity, and the resolution and sensitivity are improved by introducing this structure.
- the total of units (groups) forming the main chain, side chain and terminal constituting the copolymer is calculated as 1.
- R 1 is a divalent group derived from a divinyl compound, and when the divinyl compound is divinylbenzene, R 1 is a phenylene group.
- the alkali-soluble resin component of the component includes a carboxyl group-containing copolymer (b) obtained by reacting a polyol compound and a polyvalent carboxylic acid, and has an acid value of 50 to 200 mgKOH / g.
- the carboxyl group-containing copolymer (b) preferably has an acid value of 50 to 200 mg KOH / g and a weight average molecular weight of 3,000 to 40,000.
- the carboxyl group-containing copolymer (b) is a main component that imparts alkali solubility to the alkali-soluble resin component. Therefore, the carboxyl group-containing copolymer (b) is preferably contained in an amount of 10 to 30 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B).
- the alkali-soluble resin component of the component has an acid value that can provide alkali-solubility after curing.
- the alkali-soluble resin component of component B) may consist only of the carboxyl group-containing copolymer (b), but in order to adjust various physical properties required for the resin composition, the carboxyl group-containing copolymer ( In obtaining an alkali-soluble resin component containing b), an unsaturated compound (c) containing at least one photopolymerizable ethylenically unsaturated bond in one molecule and an epoxy resin (d) are present in the raw material. These are preferably copolymerized or polymerized or mixed, preferably copolymerized.
- the amount of the carboxyl group-containing compound used is adjusted so that the acid value of the alkali-soluble resin component falls within the above range. If either the polyol compound or the polyvalent carboxylic acid has an unsaturated bond, copolymerization with the unsaturated compound (c) becomes possible, and the epoxy resin (d) is an OH group of the polyol compound and the polyvalent carboxylic acid or Because it is reactive with COOH groups, it is believed that at least a portion is copolymerized.
- the polyol compound for obtaining the carboxyl group-containing copolymer (b) is preferably one having two hydroxyl groups in the molecule from the viewpoint of increasing the molecular weight during the polymerization reaction.
- those having, for example, a symmetrical molecular structure in which the reactivity with two acid anhydride groups in the acid dianhydride is equal are preferable.
- polyol compound examples include ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4 -Hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, bis (4-hydroxyphenyl) dimethylsilane, 4 , 4′-biphenol, phenol novolak, cresol novolak, or a compound in which part of phenol novolak or cresol novolak is glycidyl ether.
- (meth) acrylic acid adduct has a polymerizable unsaturated bond and an alkali-soluble carboxyl group in the same molecule after the reaction with the polyvalent carboxylic acid, and thus is preferable for improving the exposure sensitivity and increasing the resolution.
- a resin having a fluorene skeleton in the unit structure (hereinafter referred to as a fluorene skeleton-containing resin) is preferable in order to develop excellent heat resistance, and 30% by weight in the carboxyl group-containing copolymer.
- a fluorene skeleton-containing resin a resin having a fluorene skeleton in the unit structure
- 30% by weight in the carboxyl group-containing copolymer Preferably 50 weight% or more is effective in the heat resistant expression of a resin composition.
- the fluorene skeleton-containing resin is a resin having a fluorene skeleton obtained by reacting bisphenol fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.
- bisphenol fluorene epoxy (meth) acrylate By reacting bisphenolfluorene type epoxy (meth) acrylate with a polyvalent carboxylic acid or an acid anhydride thereof, alkali-solubility can be achieved.
- polyvalent carboxylic acids examples include polyvalent carboxylic acids, acid anhydrides, acid chlorides, and the like, and acid anhydrides are preferable.
- the polyvalent carboxylic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, pyromellitic acid, benzophenone tetracarboxylic acid.
- An acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, etc. can be mentioned, but at least a part is preferably a tetracarboxylic acid or an acid dianhydride. These can be used alone or in combination of two or more.
- the reaction between a polyol compound such as epoxy (meth) acrylate and a polyvalent carboxylic acid can be carried out by a known method.
- the polycarboxylic acid used is preferably a polybasic carboxylic acid having 3 or more basic acids in order to make the obtained fluorene skeleton-containing resin have an acid value of 10 mg KOH / g or more and express sufficient alkali solubility. It is good that it is an acid anhydride of these or a mixture thereof.
- acrylates are typical examples.
- the acrylates include those having a hydroxyl group such as polyethylene glycol (meth) acrylate and butanediol mono (meth) acrylate, for example, allyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, and methacryloxypropyltrimethoxysilane.
- Aliphatic (meth) acrylates such as glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibromopropyl (meth) acrylate, and alicyclic such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate
- Modified (meth) acrylates, other aromatic (meth) acrylates, phosphorus-containing (meth) acrylates and the like can be mentioned.
- bifunctional compounds such as diethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, and tetrabromobisphenol A di (meth) acrylate are exemplified.
- trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol Trifunctional or higher functional compounds such as penta (meth) acrylate and urethane tri (meth) acrylate are exemplified.
- the caprolactone, propylene oxide, modified ethylene oxide, etc. can be used similarly.
- other polymerizable monomers for example, monofunctional compounds such as vinyl compounds such as vinyl acetate, vinyl caprolactam, vinyl pyrrolidone, and styrene can be used as necessary.
- a polyester resin, a polyvinyl resin, etc. can be used if necessary.
- these monofunctional compounds, bifunctional compounds, trifunctional or higher functional compounds and their modified products or resins only one of them can be used alone, and of course, two or more can be used in combination. .
- the average number of ethylenically unsaturated bonds per molecule is preferably 1.5 or more.
- the photosensitive resin composition of the present invention requires not only alkali solubility but also excellent photocurability, that is, high sensitivity, two polymerizable double bonds per molecule (two (Functional) or more, more preferably, it is preferable to blend a resin or monomer having three (trifunctional) or more.
- the amount of the monomer (c) containing at least one photopolymerizable ethylenically unsaturated bond in one molecule is 3 to 25 with respect to 100 parts by weight of the total of the above components (A) and (B). It is preferably in the range of parts by weight.
- examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin.
- epoxy resins such as alicyclic epoxy resins, compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, etc. It is done.
- the amount of the epoxy resin used is preferably within a range where the alkali-soluble property of the alkali-soluble resin is maintained, and is 10 to 35 with respect to 100 parts by weight of the total of the components (A) and (B). It is preferable to blend in the range of parts by weight.
- Examples of the photopolymerization initiator (C) include radical generation types such as Michler's ketone, and cation generation types such as triarylsulfonium salts and diaryliodonium salts. These may be used alone or in combination of two or more.
- the amount of the photopolymerization initiator used is in the range of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight as a total of the components (A), (B) and (C). It is good to mix with. If it exceeds 10 parts by weight, the light absorption ratio increases, and light may not penetrate to the lower part.
- photopolymerization initiators examples include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Acetophenones such as phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.
- benzoins such as benzoin, benzoin methyl ether, benzo
- Anthraquinones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide It is done.
- photosensitization such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like.
- photosensitizers can be used alone or in combination of two or more thereof.
- the photosensitizer is preferably used in the range of 10 to 70% by weight based on the photopolymerization initiator.
- the photosensitive resin composition of the present invention one of inorganic fillers such as silica, alumina, titanium oxide, boron nitride or the like is used for the purpose of reducing the thermal expansion of the cured product and improving the elastic modulus and hygroscopicity. You may mix
- the photosensitive resin composition of the present invention includes, as necessary, a bromine-based compound, a phosphorus-based epoxy resin curing accelerator, a polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, and a flame retardant. Additives such as compounds and antimony can be blended.
- a rubber component such as polybutadiene may also be added as an auxiliary for surface roughening with a permanganate solution or the like.
- curing agent, solvent soluble resin, etc. can also be mix
- the solvent-soluble resin is preferably a polyphenylene ether resin that is excellent in compatibility with the polyfunctional vinyl copolymer. Polyphenylene ether resins are excellent in dielectric properties as well as heat resistance of cured products.
- Examples of the epoxy resin curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds.
- Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.
- Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl.
- Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.
- the photosensitive resin composition of the present invention can be adjusted in viscosity by blending a solvent as necessary.
- the solvent must be one that dissolves the alkali-soluble resin component of the photosensitive resin composition and does not react with the resin and additives of the alkali-soluble resin component, and is particularly limited if these conditions are satisfied. It is not a thing.
- the photosensitive resin composition of the present invention can contain a solvent, a filler and the like as described above.
- the component (A), the component (B), and (C) It is preferable to contain a component in the following range. % Is wt%.
- the method for using the photosensitive resin composition of the present invention is as follows: 1) after preparing as a varnish, applying this to a target object to form an insulating resin layer, and 2) using the photosensitive resin composition in advance. There is a method in which a laminate (dry film) from which a solvent has been removed is formed and used on a supporting substrate that is peeled and removed later.
- thermosetting When used as a varnish, for example, after applying the photosensitive resin composition of the present invention adjusted to a varnish on a substrate by means of spin coating, curtain coating, etc., and forming a pattern by drying, exposure, and development, The method of thermosetting is mentioned.
- the photosensitive resin composition of the present invention is uniformly applied onto a supporting substrate, and the solvent is dried by hot air drying or the like, and then a protective film as necessary.
- the method of winding by applying is illustrated.
- the drying temperature is preferably 80 to 120 ° C. in consideration of the thermal stability and productivity of the unsaturated compound.
- the dry film resist of the present invention can be produced as described above.
- the organic solvent often remains in the resin layer after drying, the content is desirably 15% by weight or less, preferably 10% by weight or less.
- the content referred to here is a weight% that is reduced when the weight of the resin layer after drying is 100% by weight and the absolute dry weight is obtained after drying again at 200 ° C. for 30 minutes. If this exceeds 15% by weight, cold flow tends to occur.
- the thickness of the insulating resin layer after drying made of the photosensitive resin composition varies depending on the application, but is 1 to 10 ⁇ m for a liquid crystal display and 5 to 100 ⁇ m for a circuit board.
- the film thickness is 30 ⁇ m
- a 30 ⁇ m via and a 20 ⁇ m line and space can be formed.
- an isolated line and isolated dot of 20 ⁇ m can be formed at 5 ⁇ m.
- the support substrate (film) to which the photosensitive resin composition is applied is preferably a transparent substrate that transmits active light.
- the support layer that transmits active light include known polyethylene terephthalate films, polyacrylonitrile films, optical polypropylene films, and cellulose derivative films. The thinner these films are, the more advantageous in terms of image forming properties and economic efficiency, but those having a thickness of 10 to 30 ⁇ m are common because of the need to maintain the strength.
- a protective film can be laminated
- An example of such a film is a polyethylene film.
- Creation of a circuit board using a cured film of the photosensitive resin composition of the present invention creation of a multichip module, creation of a color filter for a liquid crystal display and a spacer are performed by known techniques. The process will be briefly described below.
- the protective film When there is a protective film, first the protective film is peeled off, and then the insulating resin layer is heat-pressed and laminated on the substrate surface with a hot roll laminator.
- the heating temperature at this time is 70 to 120 ° C., preferably 80 to 110 ° C.
- the temperature is lower than 70 ° C., the adhesiveness to the substrate is inferior.
- the temperature is higher than 120 ° C., the photosensitive resin layer protrudes from the side edge and the film thickness accuracy is impaired.
- the supporting substrate is peeled off and image exposure is performed with active light through a mask. Subsequently, the unexposed portion of the photosensitive resin layer is developed and removed using an alkaline aqueous solution.
- an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethylamine, tetramethylammonium hydroxide or the like can be used as the alkaline aqueous solution.
- These developers are selected according to the characteristics of the resin layer, but can be used in combination with a surfactant.
- polymerization or curing (sometimes referred to as curing by combining both) is completed by heat to obtain a cured product such as a permanent insulating film.
- thermosetting in the range of 160 to 200 ° C. is preferable in order to impart heat resistance to the resin.
- the surface of the heat-cured resin layer is flattened by buffing if necessary, then roughened by applying a known desmear process using permanganate, and then non-coated by a known means.
- Electrolytic copper plating is performed, and if necessary, electrolytic copper plating is performed to form a conductor layer. In addition, it is preferable to anneal after electrolytic copper plating. If a circuit is formed by selectively etching away the conductor layer and then repeating the process of laminating the insulating layer again, a multilayer circuit board can be formed.
- GPC gel permeation chromatography
- the molecular weight shown is the weight average molecular weight (Mw) in terms of polystyrene of the carboxyl group-containing copolymer portion excluding the unreacted raw material.
- Mw weight average molecular weight
- Polymer structure This was determined by 13C-NMR and 1H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d1 was used as a solvent and the tetramethylsilane resonance line was used as an internal standard to determine the molar fraction of the structural unit (a1).
- [Terminal phenolic hydroxyl group] It was calculated from the number average molecular weight obtained from the above GPC measurement, the amount of phenolic hydroxyl group at the terminal obtained from the results of 1H-NMR measurement and elemental analysis.
- FHPA Equivalent reaction product of fluorene bisphenol type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50 wt%, solid content converted acid value 1.28 mg KOH / g, epoxy equivalent 21300)
- BPDA biphenyltetracarboxylic dianhydride
- THPA tetrahydrophthalic anhydride
- PGMEA propylene glycol monomethyl ether acetate
- TEABr tetraethylammonium bromide
- TMPTA trimethylolpropane triacrylate
- DPHA KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- YD-134 and 128 Bisphenol A type epoxy resin (Epototo manufactured by Nippon Steel Chemical Co., Ltd.)
- PPE Polyphenylene ether (Mitsubishi Gas Chemical Co.,
- Synthesis example 1 (Polyfunctional vinyl copolymer PV-A) 159.8 g (14.4 wt%) of divinylbenzene, 93.8 g (8.5 wt%) of ethyl vinylbenzene, 223.2 g (20.1 wt%) of styrene, 632.7 g (57.0 wt%) of 2-phenoxyethyl methacrylate Then, 1081 g of toluene was put into a 3 L reactor, 56.8 g of diethyl ether complex of boron trifluoride was added at 50 ° C., and reacted for 6 hours.
- This polyfunctional vinyl copolymer ⁇ has a weight average molecular weight Mw of 8000, a molar fraction of the structural unit (a1) containing a vinyl group derived from a divinyl compound is 0.18, and a two-phenoxyethyl methacrylate derived from the terminal 2-phenoxyethyl methacrylate.
- the double bond (a2) was 0.02, and the combined molar fraction (a3) of both was 0.20.
- Synthesis example 2 (Polyfunctional vinyl copolymer PV-B) 332.0 g (26.2 wt%) of divinylbenzene, 195.0 g (15.4 wt%) of ethyl vinyl benzene, 109.6 g (8.6 wt%) of styrene, 631.1 g (49.8 wt%) of 2-phenoxyethyl methacrylate Then, 865.0 g of toluene was put into a 3 L reactor, 35.5 g of diethyl ether complex of boron trifluoride was added at 50 ° C., and reacted for 3 hours.
- polyfunctional vinyl copolymer PV-B has an Mw of 8000, a molar fraction of the structural unit (a1) containing a vinyl group derived from a divinyl compound is 0.34, and a double component derived from a terminal 2-phenoxyethyl methacrylate.
- the bond (a2) was 0.03, and the combined molar fraction (a3) of both was 0.37.
- Synthesis example 3 (Polyfunctional vinyl copolymer PV-C) 4230 g (58.6 wt%) of divinylbenzene, 169 g (2.3 wt%) of ethylvinylbenzene, 1170 g (16.2 wt%) of styrene, 1649 g (22.8 wt%) of 2,6-xylenol, 158 g of ethyl acetate, and 12745 g of toluene It was put into a 30 L reactor, and 18 g (120 mmol) of diethyl ether complex of boron trifluoride was added at 70 ° C. and reacted for 2 hours.
- Mn of the obtained polyfunctional vinyl copolymer PV-C was 2820, Mw was 10800, and Mw / Mn was 3.84.
- the amount of phenolic hydroxyl groups introduced into the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 5.8 (pieces / molecule). Further, it contained 79.2 mol% of structural units derived from divinylbenzene and 20.7 mol% in total of structural units derived from styrene and ethylbenzene.
- the molar fraction of the structural unit (a1) containing a vinyl group derived from a divinyl compound contained in the polyfunctional vinyl copolymer PV-C was 0.32.
- the copolymer PV-C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.
- Synthesis example 4 (Alkali-soluble resin solution AD-A) In a 300 ml four-necked flask equipped with a reflux condenser, 96.0 g of FHPA solution, 14.4 g of BPDA, 2.5 g of PGMEA and 0.15 g of TEABr were charged, and the mixture was stirred at 120 to 125 ° C. with heating for 2 hours, and further 60 to 62 Stirring was carried out at 8 ° C. for 8 hours to obtain an alkali-soluble resin solution AD-A containing a carboxyl group-containing copolymer resin.
- the obtained resin solution had a solid content of 56.5 wt%, an acid value (converted to a solid content) of 90.3 mg KOH / g, an area percent of the carboxyl group-containing copolymer in the resin solution by GPC analysis was 90%, and a weight average The molecular weight was 15000.
- Synthesis example 5 (Alkali-soluble resin solution AD-B) In a 300 ml four-necked flask equipped with a reflux condenser, 96.0 g of FHPA solution, 10.8 g of BPDA, 5.6 g of THPA, 1.64 g of PGMEA, and 0.15 g of TEABr were charged and stirred at 120 to 125 ° C. for 2 hours while heating. Further, the mixture was heated and stirred at 60 to 62 ° C. for 8 hours to obtain an alkali-soluble resin solution AD-B containing a carboxyl group-containing copolymer resin.
- the obtained resin solution had a solid content of 56.5 wt%, an acid value (solid content conversion) of 88.1 mg KOH / g, an area percentage of the carboxyl group-containing copolymer in the resin solution by GPC analysis was 96%, and Mw was It was 5400.
- Synthesis example 7 (Vinyl benzyl ether compound: for comparison) 92 g of bisphenol A and 45 g of potassium hydroxide were dissolved in 200 g of dimethyl sulfoxide and 30 g of water, and 124 g of chloromethylstyrene and 0.1 g of hydroquinone were dissolved in 100 g of dimethyl sulfoxide, and this was added dropwise at 70 ° C. over 1 hour. The reaction was further continued at 70 ° C. for 2 hours. Next, a large excess of water was added to the system and extracted with benzene. The benzene layer was washed with a sodium hydroxide aqueous solution and distilled water, neutralized and dried. After distilling off benzene, recrystallization with ethanol (yield 90%) gave a vinylbenzyl ether compound (VB) represented by the following formula (3).
- Example 1 (Preparation of resin composition) 55 parts by weight of the alkali-soluble resin solution AD-A obtained in Synthesis Example 4 in terms of resin component, 10 parts by weight of trimethylolpropane triacrylate (TMPTA) as an unsaturated compound, and Synthesis Example 1 as a polyfunctional vinyl copolymer 7 parts by weight of the polyfunctional vinyl copolymer PV-A obtained in 1 above and 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one (start) as a photopolymerization initiator 2 parts by weight of agent A), 26 parts by weight of epoxy resin (Epototo YD-134 manufactured by Nippon Steel Chemical Co., Ltd.), 0.04 parts by weight of sensitizer (EABF manufactured by Hodogaya Chemical Co., Ltd.) and 100 parts by weight of ethyl acetate Were mixed with a stirrer for 1 hour to prepare a resin composition solution to prepare a photosensitive resin composition.
- the protective film was peeled off from the dry film resist and laminated at 80 ° C., a transfer pressure of 3 kgf / cm 2 , and a transfer speed of 25 cm / min. Thereafter, the polyester film was cooled and peeled to form a photosensitive resin layer having a thickness of 30 ⁇ m on the conductor circuit pattern.
- the substrate was washed with water for 1 minute, and then treated with N-466 neutralized solution at room temperature for 5 minutes to remove the residue of the surface potassium permanganate solution. Furthermore, after washing with water for 1 minute, washing with an ultrasonic cleaner was performed for 10 minutes, and drying was performed at 80 ° C. for 1 hour, thereby forming an anchor portion anchored on the surface of the insulating layer.
- the polyester film was cooled and peeled to form an insulating layer having a thickness of 30 ⁇ m on the aluminum vapor deposited wafer.
- UV light is applied under conditions of 250 mJ / cm 2 with an ultra-high pressure mercury lamp (manufactured by Hitech Co., Ltd., illuminance 11 mJ / cm 2 , I-line standard) through a negative mask provided with a test piece pattern on the insulating layer of the wafer.
- a 1.2% tetramethylammonium hydride solution is used as a developer, and after developing for 1 minute until the aluminum vapor deposited wafer is exposed while swinging at 28 ° C., 3.0 kg / cm
- a pure water rinse was performed at a pressure of 2 for 30 seconds to form various test pieces.
- thermosetting was performed in an air atmosphere at 180 ° C. for 90 minutes to obtain a cured insulating film.
- the test pieces thus obtained were used for various physical property measurements.
- sensitivity measuring step tablet 21 stages of Kodak
- an ultra-high pressure mercury lamp Hitech, Illuminance 11 mJ / cm 2
- a conductor circuit pattern is exposed while swinging at 28 ° C. using a 1.2% tetramethylammonium hydride solution as a developer.
- a portion of the exposed portion that is not removed after 30 minutes of pure water rinsing at a pressure of 3.0 kg / cm 2 is represented by a number (number of steps). The sensitivity was expressed by the obtained number.
- Examples 2 to 7, Comparative Examples 1 to 3 A photosensitive resin composition and a dry film were prepared in the same manner as in Example 1 using the alkali-soluble resin component, unsaturated compound, epoxy resin, and other resins shown in Table 1, and various tests were performed. The results are summarized in Table 1.
- (A) component, (B) component and (C) component are components corresponding to (A) component, (B) component and (C) component of the present invention (components for comparison and subcomponents).
- the blending amount is in parts by weight.
- the present invention it is possible to provide a photosensitive resin composition which is excellent in low dielectric constant and low dielectric loss tangent, has good workability, and does not impair photocurability, developability and other development characteristics. From this photosensitive resin composition, it is possible to provide a multilayer printed wiring board having a cured film obtained by curing it as an interlayer insulating film, and a dry film resist provided with a coating film of the photosensitive resin composition. Moreover, the photosensitive resin composition and dry film resist of the present invention are excellent in handleability and can be used as an interlayer insulating film or a solder resist film of a printed wiring board by being cured.
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Abstract
Description
(B)成分:ポリオール化合物と多価カルボン酸類とを反応させて得られるカルボキシル基含有共重合体(b)を含み、酸価が50~200mgKOH/gであるアルカリ可溶性樹脂成分、及び
(C)成分:光開始剤
を含む感光性樹脂組成物であって、(A)成分、(B)成分及び(C)成分の合計に対する(A)成分の配合量が1~98.9wt%、(B)成分の配合量が98.9~1wt%、(C)成分の配合量が0.1~10wt%であることを特徴とするアルカリ現像可能な感光性樹脂組成物に関する。
本発明の感光性樹脂組成物は、溶剤可溶性多官能ビニル共重合体(以下、(A)成分、又は多官能ビニル共重合体ともいう)と、(B)成分としてのアルカリ水溶液による現像が可能なアルカリ可溶性樹脂成分主たる成分とする。本明細書中、主たる成分とは50wt%以上、好ましくは80wt%以上含むことをいう。このアルカリ可溶性樹脂成分は、露光後においてアルカリ水溶液による現像が可能となる樹脂を与える成分を含有していれば特に限定されるものではないが、光で重合可能な樹脂(樹脂の他、モノマー等の樹脂となる成分を含む意味である)を含有することが好ましい。以下の説明においては、感光性樹脂組成物中の多官能ビニル共重合体を除く樹脂又は樹脂形成成分を単にアルカリ可溶性樹脂と称することもある。
(A)成分:1~50%、好ましくは5~24%
(B)成分:50~98%、好ましくは75~94%
(C)成分:0.1~10%、好ましくは0.5~5%
得られた樹脂溶液の約1g強を、ガラスフィルターW0(g)に含浸させて秤量W1(g)し、160℃にて2時間加熱した後の重量W2(g)から次式により求めた。
固形分濃度(重量%)=100×(W2-W0)/(W1-W0)
[酸価]
得られた樹脂溶液を、ジオキサン-エタノール等量混合溶液にいれ、フェノールフタレインを指示薬として1/10N-KOHエタノ-ル(50%)水溶液で滴定して求めた。
[分子量]
テトラヒドロフランを展開溶媒としてRI(屈折率)検出器を備えたゲルパーミエーションクロマトグラフィー(GPC)により求めた。示した分子量は、未反応原料を除いたカルボキシル基含有共重合体部分のポリスチレン換算の重量平均分子量(Mw)である。
[ポリマーの構造]
日本電子製JNM-LA600型核磁気共鳴分光装置を用い、13C-NMR及び1H-NMR分析により決定した。溶媒としてクロロホルム-d1を使用し、テトラメチルシランの共鳴線を内部標準として使用し、構造単位(a1)のモル分率を求めた。
[末端フェノール性水酸基]
上記のGPC測定より得られる数平均分子量と1H-NMR測定と元素分析の結果より得られる末端のフェノール性水酸基量とから算出した。
FHPA:フルオレンビスフェノール型エポキシ樹脂とアクリル酸との等当量反応物(新日鐵化学社製、ASF-400の溶液:固形分濃度50wt%、固形分換算の酸価1.28mgKOH/g、エポキシ当量21300)
BPDA:ビフェニルテトラカルボン酸二無水物
THPA:テトラヒドロ無水フタル酸
PGMEA:プロピレングリコールモノメチルエーテルアセテート
TEABr:テトラエチルアンモニウムブロミド
TMPTA:トリメチロールプロパントリアクリレート
DPHA:KAYARAD DPHA(日本化薬株式会社製)
YD-134及び128:ビスフェノールA型エポキシ樹脂(新日鐵化学株式会社製エポトート)
PPE:ポリフェニレンエーテル(三菱ガス化学株式会社製、極限粘度0.45品)
(多官能ビニル共重合体 PV-A)
ジビニルベンゼン159.8g(14.4wt%)、エチルビニルベンゼン93.8g(8.5wt%)、スチレン223.2g(20.1wt%)、2-フェノキシエチルメタクリレート632.7g(57.0wt%)、トルエン1081gを3Lの反応器内に投入し、50℃で56.8gの三フッ化ホウ素のジエチルエーテル錯体を添加し、6時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、室温で反応混合液を大量のメタノールに投入し、重合体を析出させた。得られた重合体をメタノールで洗浄し、濾別、乾燥、秤量して、多官能ビニル共重合体PV-Aを340.8g(収率:30.7wt%)得た。この多官能ビニル共重合体αの重量平均分子量Mwは8000で、ジビニル化合物由来のビニル基を含有する構造単位(a1)のモル分率は0.18、末端の2-フェノキシエチルメタクリレート由来の二重結合(a2)は0.02、両者を合わせた合計のモル分率(a3)は0.20であった。
(多官能ビニル共重合体 PV-B)
ジビニルベンゼン332.0g(26.2wt%)、エチルビニルベンゼン195.0g(15.4wt%)、スチレン109.6g(8.6wt%)、2-フェノキシエチルメタクリレート631.1g(49.8wt%)、トルエン865.0gを3Lの反応器内に投入し、50℃で35.5gの三フッ化ホウ素のジエチルエーテル錯体を添加し、3時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、室温で反応混合液を大量のメタノールに投入し、重合体を析出させた。得られた重合体をメタノールで洗浄し、濾別、乾燥、秤量して、多官能ビニル共重合体PV-Bを564g(収率:44.5wt%)得た。この多官能ビニル共重合体PV-BのMwは8000で、ジビニル化合物由来のビニル基を含有する構造単位(a1)のモル分率は0.34、末端の2-フェノキシエチルメタクリレート由来の二重結合(a2)は0.03、両者を合わせた合計のモル分率(a3)は0.37であった。
(多官能ビニル共重合体 PV-C)
ジビニルベンゼン4230g(58.6wt%)、エチルビニルベンゼン169g(2.3wt%)、スチレン1170g(16.2wt%)、2,6-キシレノール1649g(22.8wt%)、酢酸エチル158g、トルエン12745gを30Lの反応器内に投入し、70℃で18g(120ミリモル)の三フッ化ホウ素のジエチルエーテル錯体を添加し、2時間反応させた。重合溶液を1-ブタノール53.3gで停止させた後、室温で反応混合液を大量のn-へキサンに投入し、多官能ビニル共重合体を析出させた。得られた共重合体をn-へキサンで洗浄し、濾別、乾燥、秤量して、多官能ビニル共重合体PV-Cを3948g(収率:70.9wt%)得た。
(アルカリ可溶性樹脂溶液 AD-A)
還留冷却器付き300ml四つ口フラスコ中にFHPA溶液96.0gと、BPDA14.4g、PGMEA2.5g及びTEABr0.15gを仕込み、120~125℃に加熱下に2時間撹拌し、更に60~62℃にて8時間の加熱撹拌を行って、カルボキシル基含有共重合樹脂を含むアルカリ可溶性樹脂溶液AD-Aを得た。得られた樹脂溶液の固形分は56.5wt%、酸価(固形分換算)は90.3mgKOH/g、GPC分析による樹脂溶液中のカルボキシル基含有共重合体の面積%は90%、重量平均分子量は15000であった。
(アルカリ可溶性樹脂溶液 AD-B)
還留冷却器付き300ml四つ口フラスコ中にFHPA溶液96.0gと、BPDA10.8g、THPA5.6g、PGMEA1.64g及びTEABr0.15gを仕込み、120~125℃に加熱下に2時間撹拌し、更に60~62℃にて8時間の加熱撹拌を行って、カルボキシル基含有共重合樹脂を含むアルカリ可溶性樹脂溶液AD-Bを得た。得られた樹脂溶液の固形分は56.5wt%、酸価(固形分換算)は88.1mgKOH/g、GPC分析による樹脂溶液中のカルボキシル基含有共重合体の面積%は96%、Mwは5400であった。
(アルカリ可溶性樹脂溶液 AD-C)
エチルカルビトールアセテート中において、エポキシ当量が220で、かつ1分子中に平均して7個のフェノール残基と、エポキシ基を有するクレゾールノボラック型エポキシ樹脂のエポキシ基1モルに対し、アクリル酸を1モルの割合で反応させて得られた反応物に、THPAを0.6モルの割合で反応させ、カルボキシル基含有共重合樹脂を含むアルカリ可溶性樹脂溶液AD-Cを得た。得られた樹脂溶液の固形分は66.7wt%の粘ちょうな液体であり、樹脂分の酸価は88mgKOH/gであった。
(ビニルベンジルエーテル化合物:比較用)
ビスフェノールA92g、水酸化カリウム45gをジメチルスルホキシド200g、水30g中に溶解し、これにクロルメチルスチレン124g、ハイドロキノン0.1gをジメチルスルホキシド100gに溶解したものを、70℃で1時間かけて滴下し、さらに70℃で2時間反応を続けた。次に、系内に大過剰の水を加え、ベンゼンで抽出した。ベンゼン層は、水酸化ナトリウム水溶液、蒸留水で洗浄、中和、乾燥した。ベンゼン溜去後、エタノールで再結晶し(収率90%)、下記式(3)で示されるビニルベンジルエーテル化合物(VB)を得た。
(樹脂組成物の調製)
前記合成例4で得られたアルカリ可溶性樹脂溶液AD-Aを樹脂成分換算で55重量部、不飽和化合物としてトリメチロールプロパントリアクリレート(TMPTA)10重量部、多官能ビニル共重合体として合成例1で得られた多官能ビニル共重合体PV-Aを7重量部、光重合開始剤として2-メチル-1-[4-(メチルチオ)フェニル]-2-モノフォリノプロパン-1-オン(開始剤A)を2重量部、エポキシ樹脂(新日鐵化学株式会社製エポトートYD-134)を26重量部、増感剤(保土ヶ谷化学工業製EABF)を0.04重量部と酢酸エチル100重量部とを混合し、攪拌機により1時間、溶解させて樹脂組成物溶液を調製し感光性樹脂組成物を調製した。
上記のように調整した樹脂組成物溶液をダイコーターにより厚み25μm、幅600mmのポリエステルフィルムに塗布し、80~120℃の温度範囲で設定した連続4段乾燥炉中で乾燥し、残存溶剤率2.3%、膜厚30μmの絶縁樹脂層を得た。その乾燥塗膜上に厚さ60μmのポリエチレン製保護フィルムをラミネートし、ドライフィルムレジストを作製した。
市販の0.8mm厚のガラスエポキシ基板上の導体回路パターンを黒化処理した後、上記ドライフィルムレジストから保護フィルムを剥がし、80℃、転写圧力3kgf/cm2、転写速度25cm/分でラミネートした後、ポリエステルフィルムを冷却後剥離して、導体回路パターン上に30μm厚の感光性樹脂層を形成した。次に、上記パネルの感光性樹脂層上にバイアホールパターンを設けたネガ型マスクを介して超高圧水銀ランプ(ハイテック社製、照度11mJ/cm2、I線基準)で250mJ/cm2 の条件で紫外線照射による露光を行った後、1.2%テトラメチルアンモニウムヒドリド溶液を現像液として使用し、28℃で揺動しながら導体回路パターンが露出するまで1分間の現像の後、3.0kg/cm2の圧力で純水リンスを30秒間行い、直径30μmのバイアホールを形成した。引き続き、空気雰囲気下で180℃、60分の条件で熱硬化させ絶縁膜を得た。
得られた絶縁膜の表面を♯1000の紙やすりで3g/cm2相当バフ研磨した後、荏原電産デスミアプロセスに従い、DI-464の50%水溶液を用い液温70℃の条件で5分間浸漬して表面を膨潤させて直ちに水洗1分、50℃での湯洗2分を行った後、過マンガン酸カリウム系の粗化液PM‐465A(50g/l)、PM‐465B(15%)を用い液温60℃の条件で5分間浸漬させ表面を祖化した。引き続き水洗を1分間行った後、表面の過マンガン酸カリウム液の残渣を除去するためにN‐466中和液を用い室温にて5分間処理した。更に、水洗1分の後に超音波洗浄器により10分間の洗浄を行い、80℃で1時間乾燥することで絶縁層の表面に祖化されたアンカー部分を形成した。
次に上記基板を奥野製薬工業株式会社OPCプロセスにより無電解銅メッキを行った後、上村工業株式会社ピロブライトプロセスにて電流密度2~2.5A/dm2で電解メッキを行い、ピンホールのない厚さ18μmの析出メッキを形成し、更に、110℃の条件で60分間、次いで180℃の条件で60分間熱処理を行うことで、上層に銅箔導体層が形成された絶縁膜を形成した。
引き続き、形成された導体上に周知のエッチングレジストを形成して不要部分の銅を除去し、レジストを溶解することにより、メッキバイアホールを有する多層プリント配線板が得られた。
上記のドライフィルムの乾燥した塗膜表面に指を軽く押しつけ、指に対する張り付き程度を以下の基準で評価した。
A:全く張り付きなし
B:殆ど張り付きなし
C:ほんの僅かに張り付きあり
×:張り付きあり
上記のドライフィルムを黒化処理銅箔上にラミネートした後、感度測定用ステップタブレット(コダック21段)を設置し、このステップタブレットを通して、超高圧水銀ランプ(ハイテック社製、照度11mJ/cm2、I線基準)で250mJ/cm2の条件で紫外線照射による露光を行った後、1.2%テトラメチルアンモニウムヒドリド溶液を現像液として使用し、28℃で揺動しながら導体回路パターンが露出するまで1分間の現像の後、3.0kg/cm2の圧力で純水リンスを30秒間行った後の露光部分の除去されない部分を数字(ステップ数)で表す方法(ステップ数が大きいほど感光特性が良好)により測定し、その得られた数字で感度を表した。
硬化した絶縁膜を動的粘弾性法を用いて測定した。
[誘電率、誘電正接(Tanδ)]
硬化した絶縁膜を測定装置としてインピーダンスアナライザーHP4291(アジレントテクノロジー社製)を用いて、1GHzで測定を行なった。
[密着性]
JIS-C6481に従って絶縁膜上に形成された銅箔の90度ピール試験を行い、引き剥がし強さ(kg/cm)を測定した。
上記の硬化膜上に銅メッキが施された基板を試験片として、その試験片をプレッシャークッカー装置内に投入し、温度121℃、圧力2気圧、湿度100%の雰囲気下で200時間放置後、その層間絶縁膜の状態を目視により観察し、以下の基準に従い評価した。
A:全く変化が認められないもの
B:ほんの僅か変化しているもの
C:顕著に変化しているもの
×:塗膜が膨潤して剥離したもの
上記の硬化膜上に銅メッキが施された基板を試験片として、JIS-C6481の試験方法に従って、260℃のはんだ槽に30秒浸漬後、粘着テープによるピーリング試験を計3サイクル行い、塗膜状態を目視により観察し、以下の基準に従い評価した。
A:3サイクル後も塗膜に変化がないもの
B:3サイクル後に僅かに変化しているもの
C:2サイクル後に変化しているもの
×:1サイクル後に剥離が生じているもの
アルカリ可溶性樹脂成分、不飽和化合物、エポキシ樹脂、その他樹脂を表1に示す配合として、実施例1と同様に感光性樹脂組成物、ドライフィルムを作成し、各種試験を行った。結果をまとめて表1に示す。表中、(A)成分、(B)成分及び(C)成分は、本発明の(A)成分、(B)成分及び(C)成分に対応する成分(比較のための成分、副成分を含む)であり、配合量は重量部である。
Claims (5)
- (A)成分:ジビニル化合物(a)20~99モル%及びモノビニル化合物(b)80~1モル%を共重合して得られる共重合体であって、ジビニル化合物(a)に由来する下記式(a1)で表される未反応のビニル基を含有する構造単位の含有量が10~90モル%である溶剤可溶性多官能ビニル共重合体、
式中、R1は炭素数6~30の芳香族炭化水素基を示す。
(B)成分:ポリオール化合物と多価カルボン酸類とを反応させて得られるカルボキシル基含有共重合体(b)を含み、酸価が50~200mgKOH/gであるアルカリ可溶性樹脂成分、及び
(C)成分:光開始剤
を含む感光性樹脂組成物であって、(A)成分、(B)成分及び(C)成分の合計に対する(A)成分の配合量が1~98.9wt%、(B)成分の配合量が98.9~1wt%、(C)成分の配合量が0.1~10wt%であることを特徴とするアルカリ現像可能な感光性樹脂組成物。 - 溶剤可溶性多官能ビニル共重合体が、末端にフェノール性水酸基を有し、その導入量が2.2個/分子以上であることを特徴とする請求項1に記載の感光性樹脂組成物。
- カルボキシル基含有共重合体(b)が、一つ以上のビニル基を有するポリオール化合物と多価カルボン酸類とを反応させて得られるカルボキシル基含有共重合体であって、重量平均分子量が3,000~40,000、酸価が50~200mgKOH/gである請求項1に記載の感光性樹脂組成物。
- 剥離可能な支持基材上に感光性樹脂層が設けられたドライフィルムレジストにおいて、感光性樹脂層が請求項1~4のいずれかに記載の感光性樹脂組成物から構成されていることを特徴とするドライフィルムレジスト。
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JP2019194307A (ja) * | 2018-04-27 | 2019-11-07 | パナソニックIpマネジメント株式会社 | 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板 |
JP2021076643A (ja) * | 2019-11-06 | 2021-05-20 | 昭和電工マテリアルズ株式会社 | 感光性樹脂組成物、及びそれを用いた配線層と半導体装置 |
JP2021182149A (ja) * | 2016-04-14 | 2021-11-25 | 旭化成株式会社 | 感光性樹脂組成物及び硬化レリーフパターンの製造方法 |
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US10338468B2 (en) * | 2014-09-24 | 2019-07-02 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin composition, photosensitive resin laminate, resin pattern production method, cured film, and display device |
JP2022000683A (ja) * | 2019-12-13 | 2022-01-04 | 旭化成株式会社 | 感光性樹脂組成物、感光性樹脂組成物を用いた転写フィルム |
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