TW201329618A - Photosensitive resin composition, and dry film resist - Google Patents

Abstract

Provided are: a photosensitive resin composition which can be developed with an alkaline aqueous solution and enables the easy formation of a cured film that is highly sensitive, has various properties including an insulation property and heat resistance, and also has excellent dielectric properties; and a dry film. An alkali-developable photosensitive resin composition comprising a component (A) which is a solvent-soluble polyfunctional vinyl copolymer produced by copolymerizing 20-99 mol% of a divinyl compound (a) with 80-1 mol% of a monovinyl compound (b) and having a vinyl group derived from the divinyl compound (a) in a side chain, a component (B) which is an alkali-soluble resin component comprising a carboxyl-group-containing copolymer (b) produced by reacting a polyol compound with a polycarboxylic acid, and a component (C) which is a photoinitiator, wherein the contents of the component (A), the components (B) and the component (C) are 1-98.9 wt%, 98.9-1 wt% and 0.1-10 wt%, respectively, relative to the total amount of the components (A) to (C).

Description

Photosensitive resin composition and dry film resist

The present invention relates to a photosensitive resin composition excellent in high sensitivity, high insulating properties, dielectric properties, heat resistance, and the like, and a dry film resist using the photosensitive resin composition.

In recent years, in the field of electronic equipment, it has been pointed out that the size and density of the mounting method are significantly reduced, and the material is required to have more excellent characteristics. For example, an insulating resin material used in a printed wiring board is also required to have heat resistance, fine workability, electronic characteristics, and the like. An effective means for microfabrication of an insulating resin material is known to be patterned by development. Therefore, when a photosensitive resin composition is used, high sensitivity, adhesion to a substrate, electronic properties, and resistance are required. Various properties such as plating property, heat resistance, and dimensional stability. In particular, in the electronic characteristics, there is a disadvantage that the dielectric characteristics in the high frequency region are deteriorated, and it is not possible to correspond to a material of a multilayer printed wiring board on which a high frequency circuit is mounted.

In addition, the photosensitive resin composition used in such a field generally contains a polymerizable oligomer having an unsaturated double bond, a polymerizable monomer, and a photopolymerization initiator as essential components. The polymerizable oligomer which is mainly used as the photosensitive component is a polyester acrylate, a urethane acrylate, an epoxy acrylate, etc., and since these polymerizable oligomers have a polymerizable unsaturated group, The radical of the photopolymerization initiator is reacted with another polymerizable monomer, and a cured product is formed by crosslinking.

In general, these polymerizable compounds have a small molecular weight and are instantly hardened by light irradiation, and residual stress is generated in the coating film, which causes a problem of adhesion to the substrate and deterioration of mechanical properties. In order to solve this problem, the polymerization of the polymerizable compound is also reviewed. However, when adjusting the viscosity of the coatable layer, a large amount of solvent or a reactive diluent is required, so that the photosensitive resin composition lacks mechanical strength and chemical resistance. Wait. Further, the solubility in the alkali developer is lowered by the high molecular weight, which causes problems such as development failure. Further, the dry film coated with the photosensitive resin composition is required to be free from cracking, wrinkles, and the like in the state before being attached to the substrate, and the followability and flatness to the substrate are required at the time of attachment.

In Patent Document 1, it is attempted to improve dielectric properties by using an alkali developable photosensitive polyfunctional vinyl compound. Further, in Patent Documents 2 and 3, a solvent-soluble polyfunctional vinyl copolymer is disclosed, but alkali developability is not obtained.

[Practical Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-27145

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-123873

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-213443

An object of the present invention is to provide a pattern which can be easily formed by development with an alkaline aqueous solution, has high sensitivity, and has various properties such as insulation properties and heat resistance, and which is excellent in dielectric properties which are difficult to achieve at the same time as conventional properties. Shape thin A photosensitive resin composition of a film and a dry film resist.

The present invention relates to an alkali-developable photosensitive resin composition comprising the component (A): a divinyl compound (a) 20 to 99 mol% and a monovinyl compound (b) 80 to 1 mol Copolymerization of the obtained copolymer, solvent-soluble polyfunctional vinyl group containing 10 to 90 mol% of the unreacted vinyl structural unit represented by the following formula (a1) derived from the divinyl compound (a) Copolymer, component (B): a carboxyl group-containing copolymer (b) obtained by reacting a polyol compound with a polyvalent carboxylic acid, an alkali-soluble resin component having an acid value of 50 to 200 KOH/g, and (C) component: light The photosensitive resin composition of the initiator is characterized in that the amount of the component (A) is from 1 to 98.9 wt% based on the total amount of the component (A), the component (B), and the component (C). The compounding amount of the component B) is 98.9 to 1% by weight, and the compounding amount of the component (C) is 0.1 to 10% by weight.

(wherein R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms)

The solvent-soluble polyfunctional vinyl copolymer has a phenolic hydroxyl group at the terminal, and the amount thereof is 2.2 or more, or the solvent is soluble. The polyfunctional vinyl copolymer preferably has an end group containing an unsaturated bond represented by the following formula (a2) at the terminal.

(here, R ² represents a hydrocarbon group having 1 to 18 carbon atoms which may contain an etheric oxygen atom or a sulfur-containing sulfur atom, and R ³ represents hydrogen or a methyl group)

Further, the weight average molecular weight of the above carboxyl group-containing copolymer (b) is preferably from 3,000 to 40,000.

Further, the present invention relates to a dry film resist which is a dry film resist provided with a photosensitive resin layer on a peelable supporting substrate, characterized in that the photosensitive resin layer is composed of the above-mentioned photosensitive resin composition Composition.

[In order to implement the invention]

The invention will be described in detail below.

The photosensitive resin composition of the present invention is a solvent-soluble polyfunctional vinyl copolymer (hereinafter referred to as (A) component or polyfunctional vinyl copolymer) or a component (B) which can be developed by an aqueous alkali solution. The soluble resin component is the main component. The main component in the present specification means 50% by weight or more, preferably 80% by weight or more. The alkali-soluble resin component is not particularly limited as long as it contains a resin which can be developed by an aqueous alkali solution after exposure, and contains a photopolymerizable resin (in addition to the resin, It is preferable to have a component formed of a resin which forms a monomer or the like. In the following description, the resin or the resin-forming component may be simply referred to as an alkali-soluble resin in addition to the polyfunctional vinyl copolymer in the photosensitive resin composition.

Further, the amount of the component (A) is from 1 to 98.9 wt%, and the amount of the component (B) is from 98.9 to 1 wt%, based on the total amount of the component (A), the component (B), and the component (C). . The compounding amount of the component (A) is preferably from 1 to 50% by weight, more preferably from 5 to 24% by weight, and when the amount of the component (A) is too small, the effect on low dielectric properties and moisture resistance is lowered. When it is too much, it is not desirable because the developability deteriorates.

The polyfunctional vinyl copolymer of the component (A) is known, and these can be used. For example, the method disclosed in JP-A-2004-123873, JP-A-2005-213443, WO2009/110453, and the like can be used as a reference. Specifically, a copolymer having a reactive graft vinyl group represented by the formula (a1) is obtained by copolymerizing a divinyl compound with at least one or more monovinyl compounds. Further, as described in the above-mentioned patent documents, it is also possible to use a terminal having a terminal other than a vinyl group introduced at the end, in particular, a compound having an unsaturated bond in the molecule such as a phenoxy methacrylate. The reformer is preferred because it can also function as a cross-linking point in addition to (a1). At this time, since the structural unit (a2) having the terminal unsaturated bond also has a vinyl group, the total molar fraction (a3) of the structural unit of the formula (a1) indicates the amount of the entire vinyl group.

The divinyl compound used herein, for example, a divinyl aromatic compound which is typically divinylbenzene or an aliphatic or alicyclic (meth) acrylate which is typical of ethylene glycol di(meth)acrylate. Classes, etc.

Further, the monovinyl compound used herein may be an olefinic double bond copolymerizable with styrene, for example, an aromatic vinyl monomer such as p-methylstyrene, acrylic acid or methyl group. An acrylic monomer such as acrylic acid, a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, an acrylic monomer such as butyl acrylate or methyl methacrylate, or α such as maleic anhydride or fumaric acid. A quinone imine monomer such as a β-vinyl unsaturated carboxylic acid, a phenyl maleimide or a cyclohexyl maleimide.

The method for producing a polyfunctional vinyl copolymer, for example, a compound selected from the group consisting of a divinyl aromatic compound, a monovinyl aromatic compound, and another monovinyl compound, is selected from a Lewis acid catalyst. It is obtained by cationic copolymerization in the presence of a co-catalyst of an ester compound. Further, when a (meth) acrylate-based divinyl group or a monovinyl compound is used, since no reaction is carried out during cationic polymerization, it can be obtained by radical polymerization in the presence of a radical catalyst such as a peroxide. .

The amount of the divinyl compound and the monovinyl compound used may be determined depending on the composition of the polyfunctional vinyl copolymer used in the present invention, and the divinyl compound is used in an amount of 20 to 99 mol%, preferably the total amount. 20~50% by mole, and more preferably 30~50% by mole. The monovinyl compound is used in an amount of 80 to 1 mol%, preferably 80 to 50 mol% of the total amount, and more preferably 70 to 50 mol%. Here, when cationic polymerization is carried out such as 2-phenoxyethyl methacrylate, the function as a terminal modifier cannot be calculated as a monomer.

The Lewis acid catalyst used in the manufacture of the polyfunctional vinyl copolymer is a compound formed by a metal ion (acid) and a ligand (base), which is acceptable. The electronic pair can be used without any special restrictions. In terms of controlling the molecular weight, the molecular weight distribution, and the polymerization activity, it is preferred to use a boron trifluoride ether (diethyl ether, dimethyl ether or the like). The Lewis acid catalyst is used in the range of 0.001 to 10 moles, preferably 0.001 to 0.01 moles, per mole of the monomer compound 1 mole. When the amount of the Lewis acid catalyst used is too large, the polymerization rate is too large, and it is difficult to control the molecular weight distribution, so it is not desirable.

The promoter is, for example, one or more selected from the group consisting of ester compounds. Among them, in order to control the polymerization rate and the molecular weight distribution of the copolymer, it is preferred to use an ester compound having 4 to 30 carbon atoms. In terms of easy availability, it is preferred to use ethyl acetate, propyl acetate and butyl acetate. The cocatalyst is used in the range of 0.001 to 10 moles, preferably 0.01 to 1 mole, relative to the monomer compound 1 mole. When the amount of the co-catalyst used is too large, the polymerization rate is lowered and the yield of the copolymer is lowered. Further, when the amount of the catalyst used is too small, the selectivity of the polymerization reaction is lowered, and the molecular weight distribution is increased, and it is difficult to control the polymerization reaction other than the formation of a gel or the like.

Further, a catalyst used in the production of a polyfunctional vinyl copolymer by radical polymerization, for example, an azo compound typical of azobisisobutyronitrile, a benzhydryl peroxide, and a t-butyl group A monofunctional peroxide such as an oxybenzoate or a polyfunctional peroxide having two or more functionalities of 1,1-bis(t-butylperoxy)cyclohexane may be used alone or in combination of two or more. And use it.

The polyfunctional vinyl copolymer used in the present invention can be obtained by the above-described production method, and a part of the vinyl group of the divinyl compound used as a monomer must remain under polymerization. Therefore, at least two or more, preferably three or more vinyl groups are present in at least one molecule. The vinyl series is mainly It exists in the structural unit shown by the above formula (a1). Therefore, a part of the vinyl group remains without polymerization, and the crosslinking reaction can be suppressed and the solvent can be made soluble. Here, the solvent solubility means that it is soluble in toluene, xylene, THF, dichloroethane or chloroform, and specifically, in 100 g of these solvents, 5 g or more is dissolved at 25 ° C, and no gel is generated. Further, a part of the divinyl compound must be crosslinked or branched by two vinyl reactions, whereby a copolymer having a branched structure can be formed. The divinyl compound in such a portion is reacted with one of the two vinyl groups, one without remaining by polymerization, and the other portion is obtained by reacting two vinyl groups to obtain the polyfunctional ethylene used in the present invention. Base copolymer. The polymerization method for producing the polyfunctional vinyl copolymer can be produced as described above by the above-mentioned conventional methods.

The weight average molecular weight (Mw) of the polyfunctional vinyl copolymer is preferably from 1,000 to 100,000, more preferably from 5,000 to 70,000. When the amount is less than 1,000, the viscosity at the time of the photosensitive resin composition is low, and it becomes difficult to form a thick film at the time of coating, and when it is a dry film, wrinkles and the like are generated to lower the processing and handleability. In addition, when the Mw is 100,000 or more, the solubility in the composition is lowered, the appearance is poor, and the alkali solubility is lowered by the high molecular weight, which tends to deteriorate the developability.

Further, the polyfunctional vinyl copolymer is preferably a phenolic hydroxyl group derived from a polymerization additive at a partial terminal thereof or a structural unit represented by the above formula (2), and the introduction amount to the terminal of the phenolic hydroxyl group is 2.2 / More than the molecule. By introducing a phenolic hydroxyl group at the terminal, a resin composition having improved development characteristics by an alkali solution can be obtained. Further, when a phenolic hydroxyl group is introduced into a terminal of a part of the polyfunctional vinyl copolymer, the performance as an alkali-soluble resin can be exhibited. However, the calculation as a polyfunctional vinyl copolymer at this time cannot be calculated as an alkali-soluble resin. In the above formula (2), R ₂ and R ₃ have the above meanings, 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 into which a polyfunctional vinyl copolymer is introduced has a structural unit represented by the above formula (a1), and the molar fraction of the structural unit (a1) is preferably 0.1 to 0.9. Preferably, it is 0.1 to 0.5, and more preferably 0.1 to 0.3. When the molar fraction is less than 0.1, the crosslinking density of the cured product is lowered, and water resistance, mobility resistance, and heat resistance are lowered, so that it is not desired. On the other hand, when it exceeds 0.9, since the hardened material is excessively crosslinked and becomes brittle, it is not desirable. Further, as described above, in the case where the compound having an unsaturated bond in the molecule is subjected to terminal modification, the structural unit represented by the formula (a1) is substituted, and since the structural unit (a2) having the terminal unsaturated bond also has a vinyl group, Therefore, the total molar fraction (a3) of the two is preferably 0.1 to 0.9, preferably 0.1 to 0.5, and more preferably 0.1 to 0.3. The structural unit (a2) containing a terminal unsaturated bond is excellent in light reflectivity, and by introducing the structure, the resolution and sensitivity can be improved. In the calculation of the above molar fraction, the total amount of the unit (base) forming the main chain, the side chain, and the end of the copolymer was calculated to be 1.

In the formula (a1), R ¹ is derived from a divalent group of a divinyl compound, and when the divinyl compound is divinylbenzene, R ¹ is a biphenyl group.

The alkali-soluble resin component of the component (B) includes a carboxyl group-containing copolymer (b) obtained by reacting a polyol compound with 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 mgKOH/g and a weight average molecular weight of 3,000 to 40,000. The carboxyl group-containing copolymer (b) is a main component which imparts alkali solubility to an alkali-soluble resin component. Therefore, the carboxyl group-containing copolymer (b) is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total of the components (A) and (B).

The alkali-soluble resin component of the component (B) has an acid value which can impart alkali solubility after curing. The alkali-soluble resin component of the component (B) can be formed only from the carboxyl group-containing copolymer (b), and the carboxyl group-containing copolymer (b) can be obtained by adjusting various physical properties required for the resin composition. When the alkali-soluble resin component is present, the unsaturated compound (c) containing one or more photopolymerizable ethylenically unsaturated bonds in one molecule and the epoxy resin (d) are present in the raw material to cause such copolymerization or Polymerization or mixing, preferably copolymerization. At this time, the amount of the compound containing a carboxyl group is adjusted so that the acid value of the alkali-soluble resin component is in the above range. Since the polyol compound and the polyvalent carboxylic acid have an unsaturated bond, they may be copolymerized with the unsaturated compound (c), the epoxy group (d) and the polyol compound and the OH group or COOH group of the polyvalent carboxylic acid. It is reactive, so it is conceivable to carry out at least partial copolymerization.

In order to obtain the polyol compound in the above-mentioned carboxyl group-containing copolymer (b), it is preferred to have two hydroxyl groups in the molecule in terms of molecular weight increase in the polymerization reaction, and the hydroxyl group and the polyvalent carboxylic acid are preferred. The reactivity with the two acid anhydride groups in the acid dianhydride is equal, and it is preferably, for example, a structure having a symmetrical molecular structure.

Preferred specific examples of the polyol compound, such as ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, bis(4-hydroxyphenyl)one, Bis(4-hydroxyphenyl)anthracene, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)hexafluoropropane, 9,9- Bis(4-hydroxyphenyl)fluorene, bis(4-hydroxyphenyl)dimethyloxane, 4,4'-bisphenol, phenol novolac, cresol novolac, or part of phenol novolac or cresol novolac A compound in which the varnish is epoxidized and the like. Further, for example, an addition compound of a polyglycidyl ether and a (meth)acrylic acid derived from a polyol compound, an adduct of a cycloaliphatic epoxy group and a (meth)acrylic acid, and the aforementioned bisphenol The addition of an adduct of ethylene oxide or propylene oxide is preferred. In particular, when a (meth)acrylic acid adduct is reacted with a polyvalent carboxylic acid, and a polymerizable unsaturated bond and an alkali-soluble carboxyl group are contained in the same molecule, it is preferable to improve exposure sensitivity and high resolution.

When the copolymer having a carboxyl group has excellent heat resistance, a resin having an anthracene skeleton in a unit structure (hereinafter referred to as a resin containing an anthracene skeleton) is preferably used, and a carboxyl group-containing copolymer is used in an amount of 30% by weight or more. It is preferably 50% by weight or more, and is effective for having heat resistance of the resin composition.

The resin having an anthracene skeleton is more preferably a resin having an anthracene skeleton obtained by reacting a bisphenol anthracene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof. Alkali solubility can be formed by reacting a bisphenol fluorene type epoxy (meth) acrylate with a polyvalent carboxylic acid or its anhydride.

The polyvalent carboxylic acid such as a polyvalent carboxylic acid, an acid anhydride thereof, an acid chloride or the like is preferably an acid anhydride. Polyvalent carboxylic acids such as maleic acid, succinic acid, itaconic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl ortho-methylenetetrahydrophthalic acid, chlorobridge acid, methyl Tetrahydrophthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, etc., at least in part A tetracarboxylic acid or an acid dianhydride is preferred. These may be used alone or in combination of two or more.

The reaction of a polyol compound such as an epoxy group (meth) acrylate with a polyvalent carboxylic acid can be carried out by a known method. Further, in the polyvalent carboxylic acid to be used, when the acid value of the obtained ruthenium skeleton-containing resin is 10 mgKOH/g or more and has sufficient alkali solubility, it is preferably an acid anhydride of a polybasic carboxylic acid having a ternary acid or higher. a mixture of these.

When a monomer (c) containing one or more photopolymerizable ethylenically unsaturated bonds in one molecule is used, it is typically exemplified, for example, an acrylate. Acrylates such as polyethylene glycol (meth) acrylate, butanediol di (meth) acrylate, etc. having a hydroxyl group, or, for example, allyl (meth) acrylate, butoxy triethylene Alcohol (meth) acrylate, methacryloxypropyl trimethoxy decane, epoxy propyl (meth) acrylate, tetrafluoro propyl (meth) acrylate, dibromopropyl (methyl) An aliphatic (meth) acrylate such as acrylate or an alicyclic modified (meth) acrylate such as dicyclohexyl (meth) acrylate or isobornyl (meth) acrylate Other aromatic (meth) acrylates, phosphorus-containing (meth) acrylates, and the like. Further, a difunctional compound such as diethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate or tetrabromobisphenol A di(meth)acrylate. Further, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(methyl) a compound having three or more functional groups such as an acrylate, an alkyl modified dipentaerythritol penta (meth) acrylate, or a urethane tris (meth) acrylate.

Next, as the monofunctional compound, the difunctional compound, and the trifunctional or higher compound having an ethylenically unsaturated bond, a caprolactone, a propylene oxide, an ethylene oxide modified product, or the like can be used in the same manner. Further, as the other polymerizable monomer, a monofunctional compound such as a vinyl compound such as vinyl acetate, vinyl caprolactam, vinyl pyrrolidone or styrene may be used as needed. Further, a polyester resin, a polyethylene resin, or the like may be used as needed. Then, the monofunctional compound, the difunctional compound, and the trifunctional or higher compound, and the modified product or the resin may be used alone or in combination of two or more. Further, the number of the ethylenically unsaturated bonds per one molecule is preferably 1.5 or more.

In particular, in the photosensitive resin composition of the present invention, in addition to alkali solubility, when excellent photocurability, that is, high sensitivity is required, a double bond having two (difunctional) or more polymerizable groups in one molecule is blended (more Preferably, three or more (trifunctional) or higher resins or monomers are preferred. The amount of the monomer (c) containing one or more photopolymerizable ethylenically unsaturated bonds in one molecule is 100 parts by weight based on the total amount of the components (A) and (B). A range of 3 to 25 parts by weight is preferred.

When epoxy resin (d) is used, epoxy resin such as phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy resin, bisphenol epoxy resin, alicyclic epoxy resin, etc., phenyl epoxidized ether, p-butyl phenol epoxidized ether, triepoxypropyl isocyanate, epoxide A compound having at least one epoxy group, such as propyl isocyanate, allyl epoxidized propyl ether or propylene methacrylate. The amount of epoxy resin used, The blending property of the alkali-soluble resin may be maintained within a range of from 10 to 35 parts by weight based on 100 parts by weight of the total of the components (A) and (B).

The photopolymerization initiator (C) is, for example, a radical generating type such as Michler's ketone or a cation generating type such as a triarylsulfonium salt or a diaryliodonium salt. Secondly, these may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be used may be 0.1 to 10 parts by weight (preferably 1 to 5) based on 100 parts by weight of the total of the components (A) and (B) and (C). The range of weight points). When it exceeds 10 parts by weight, there is a fear that the light absorption ratio becomes large and the light cannot penetrate below.

Such photopolymerization initiators, such as benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isobutyl ether, etc.; acetophenone, 2,2- Diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenyl Propane-1 ketone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylsulfonyl)phenyl]-2-morpholinylpropan-1-one Acetophenones; anthraquinones such as 2-ethylhydrazine, 2-tert-butylhydrazine, 2-chloroindole, 2-pentylhydrazine, etc.; 2,4-diethylthiophene a thioxanthone such as ketone, 2-isopropylthioxanthone or 2-chlorothioxanthone; an acetal such as acetophenone dimethyl acetal or benzyl dimethyl acetal; a benzophenone such as ketone, 4-benzylidene-4'-methyldiphenyl sulfide or 4,4'-bismethylaminobenzophenone; 2,4,6-three A phosphine oxide such as methyl benzhydryl diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide.

Further, in addition to the photopolymerization initiator, for example, N,N-dimethyl can be combined a conventional photosensitizer such as ethyl carbamic acid benzoate, isoamyl N,N-dimethylaminobenzoate, triethanolamine or triethylamine. At this time, these photosensitizers can be used alone. It is also possible to use two or more types in combination. The photosensitizer is preferably in the range of 10 to 70% by weight based on the photopolymerization initiator.

In the photosensitive resin composition of the present invention, for the purpose of improving the low thermal expansion, the modulus of elasticity, or the hygroscopicity of the cured product, for example, one or two or more kinds of cerium oxide or aluminum oxide may be blended. Inorganic fillers such as titanium oxide and boron nitride. Further, in the photosensitive resin composition of the present invention, an epoxy resin hardening accelerator, a polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, and a bromine system as a flame retardant may be blended as needed. An additive such as a compound, a phosphorus compound or a hydrazine. Further, a rubber component such as polybutadiene may be added as an auxiliary agent for roughening the surface by a permanganate solution or the like. Further, an epoxy resin curing agent or a solvent-soluble resin may be blended, and a curing agent or a resin may be used as the alkali-soluble resin. The solvent-soluble resin is preferably a polyphenylene ether-based resin excellent in compatibility with a polyfunctional vinyl copolymer. The polyphenylene ether-based resin not only improves the heat resistance of the cured product but also has excellent dielectric properties.

An epoxy resin hardening accelerator such as an amine compound, an imidazole compound, a carboxylic acid, a phenol, a quaternary ammonium salt or a methylol group-containing compound. Thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrophenol, 3-butylcatechol, benzothiazine, and the like. Plasticizers such as dibutyl benzoate, dioctyl benzoate, tri-o-benzyl and the like. The antifoaming agent and the leveling agent are, for example, a polyfluorene type, a fluorine type, or an acrylic type compound.

The photosensitive resin composition of the present invention can also be used as a solvent To adjust its viscosity. The solvent must be an alkali-soluble resin component which can dissolve the photosensitive resin composition, and does not react with the resin and the additive of the alkali-soluble resin component, and is not particularly limited as long as the conditions are satisfied.

The photosensitive resin composition of the present invention may contain a solvent, a filler, or the like as described above, but the photosensitive resin containing the solvent and the filler may contain the above-mentioned (A) component, (B) component, and The C) component is preferred. % is wt%.

(A) Ingredients: 1~50%, preferably 5~24%

(B) Composition: 50~98%, preferably 75~94%

(C) Component: 0.1 to 10%, preferably 0.5 to 5%

The method of using the photosensitive resin composition of the present invention is, for example, 1) after the varnish is applied, the article is applied to the object of interest to form an insulating resin layer, or 2) the photosensitive resin composition is prepared. A method in which a layered body (dry film) from which a solvent is removed is applied to a support substrate which has been removed by peeling off.

When using as a varnish, for example, the photosensitive resin composition of the present invention adjusted to a varnish shape is applied onto a substrate by means of spin coating, curtain coating, or the like, and formed by drying, exposure, and development. , a method of performing thermal hardening. Further, when a dry film resist is used in advance, the photosensitive resin composition of the present invention is uniformly applied onto a support substrate, and the solvent is dried by hot air drying or the like, and then a protective film is wound up as needed. The drying temperature is preferably from 80 to 120 ° C in view of thermal stability and productivity of the unsaturated compound. Moreover, in order to prevent the epidermal expansion of the surface of the coating film during drying In the case of foaming or foaming, it is preferred to increase the temperature in multiple stages.

The dry film resist of the present invention can be produced as described above. Most of the residual organic solvent in the resin layer after drying is preferably 15% by weight or less, preferably 10% by weight or less. The content referred to herein is a weight % which is reduced by 100 wt% of the resin layer after drying and dried at 200 ° C for 30 minutes as an absolute dry weight. When the system exceeds 15% by weight, cold flow is likely to occur.

The thickness of the dried insulating resin layer formed of the photosensitive resin composition varies depending on the application, and the liquid crystal display tends to be 1 to 10 μm, and the circuit board is used in an amount of 5 to 100 μm. When the thickness of the resin layer is thinner, the resolution can be improved, and a dielectric layer and fine lines equal to or less than the thickness of the resin layer can be formed. For example, when the film thickness is 30 μm, a 30 μm layer, a line of 20 μm, and a gap can be formed. Moreover, it is also possible to form an isolated line of 20 μm or an isolated point at 5 μm.

The support substrate (film) to which the photosensitive resin composition is applied is preferably one which is transparent to permeable light. The support layer that transmits the active light is, for example, a conventional polyethylene terephthalate film, a polyacrylonitrile film, an optical device propylene film, a cellulose derivative film, or the like. The thinner the thickness of these films is advantageous in terms of image formation and economy, and it is generally 10 to 30 μm when strength or the like is required. Further, in the laminate of the present invention, the protective film may be laminated on the surface of the insulating resin layer which is not bonded to the support substrate as needed. The protective film preferably has a small enough force to adhere to the photosensitive resin composition layer to support the film, and can be easily peeled off. The film is, for example, a polyethylene film.

The preparation of the circuit board using the cured film of the photosensitive resin composition of the present invention, the formation of a multi-wafer type, the color filter for a liquid crystal display, or a spacer are carried out by a conventional technique, and the following is a circuit board. A simple explanation of the steps is made as an example.

When the protective film is provided, the protective film is first peeled off, and then heat-melted by a heat roll laminator or the like on the surface of the substrate to laminate an insulating resin layer. The heating temperature at this time is 70 to 120 ° C, preferably 80 to 110 ° C. When it is less than 70 ° C, the adhesion to the substrate is not good, and when it is more than 120 ° C, the photosensitive resin layer overflows after the side etching, and the film thickness accuracy is impaired. Next, the support substrate is peeled off and passed through a photomask to perform image exposure by active light. Then, development is performed using an aqueous alkali solution to remove the unexposed portion of the photosensitive resin layer. As the aqueous alkali solution, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine or tetramethylammonium hydroxide can be used. These developing solutions are selected to conform to the characteristics of the resin layer, but may also be used in combination with the surfactant. Next, a cured product such as a permanent insulating film which is polymerized or hardened by heat (combined as hardening) is formed. In this case, in order to impart heat resistance to the resin, it is preferred to carry out thermal curing in the range of 160 to 200 °C.

The surface of the thermosetting resin layer is planarized by polishing, as needed, and then roughened by a conventional slag removal process using permanganate, followed by conventional The method implements electroless copper plating, and electrolytic copper plating is performed as needed to form a conductor layer. Further, after electrolytic copper plating, annealing treatment is preferred. After the conductor layer is selectively etched and removed to form a circuit, the step of laminating the insulating layer is repeated to form a multilayer circuit substrate.

[Examples]

In the following, the present invention will be described in more detail by way of Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited by the Examples. Further, the evaluation of the resin in the synthesis examples described below is not limited to those shown below.

[solid concentration]

About 1 g of the obtained resin solution was impregnated into the glass filter W0 (g), weighed to W1 (g), and the weight after heating at 160 ° C for 2 hours was W2 (g), and it was obtained by the following.

Solid content concentration (% by weight) = 100x (W2-W0) / (W1-W0).

[acid value]

The obtained resin solution was added to a dioxane-ethanol equivalent mixed solution, and phenolphthalein was used as an indicator and titrated with a 1/10 N-KOH ethanol (50%) aqueous solution.

[molecular weight]

Tetrahydrofuran was used as a developing solvent, and was obtained by gel permeation chromatography (GPC) equipped with an RI (refractive index) detector. The molecular weight shown is a polystyrene-equivalent weight average molecular weight (Mw) of a portion of the carboxyl group-containing copolymer from which an unreacted raw material is removed.

[Structure of polymer]

It was determined by 13 C-NMR and 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectroscope manufactured by JEOL. Using chloroform-d1 as a solvent and using a resonance line of tetramethyl decane as an internal standard, the molar fraction of the structural unit (a1) was determined.

[terminal phenolic hydroxyl group]

The number of terminal phenolic hydroxyl groups obtained by the above-mentioned GPC measurement and the number of terminal phenolic hydroxyl groups obtained by 1H-NMR measurement and elemental analysis were calculated.

Next, the abbreviations used in the synthesis examples and examples are as follows.

FHPA: Equivalent reactant of bisphenol type epoxy resin and acrylic acid (solution of ASF-400, manufactured by Nippon Steel Chemical Co., Ltd.: solid content concentration: 50% by weight, solid content conversion acid value: 1.28 mgKOH/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 (made by Nippon Kayaku Co., Ltd.)

YD-134 and 128: bisphenol A type epoxy resin (Epotot manufactured by Nippon Steel Chemical Co., Ltd.)

PPE: Polyphenylene diene (Mitsubishi Gas Chemical Co., Ltd., special Sexual viscosity 0.45 products)

Synthesis Example 1 (Polyfunctional Vinyl Copolymer PV-A)

In a 3L reactor, 159.8 g (14.4 wt%) of divinylbenzene, 93.8 g (8.5 wt%) of ethylvinylbenzene, 223.2 g (20.1 wt%) of styrene, and 2-phenoxyethyl methacrylic acid were charged. 632.7 g (57.0 wt%) of ester and 1081 g of toluene were added, and 56.8 g of a boron trifluoride complex of boron trifluoride was added at 50 ° C to carry out a reaction for 6 hours. After the polymerization solution was stopped with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to prepare a polyfunctional vinyl copolymer PV-A 340.8 g (yield: 30.7 wt%). The polyfunctional vinyl copolymer α has a weight average molecular weight Mw of 8,000, and a structural unit (a1) containing a vinyl group derived from a divinyl compound has a molar fraction of 0.18, and a 2-phenoxyethyl group derived from the terminal. The double bond (a2) of the acrylate was 0.02, and the molar fraction (a3) of the two was 0.20.

Synthesis Example 2 (Polyfunctional Vinyl Copolymer PV-B)

In a 3L reactor, 332.0 g (26.2 wt%) of divinylbenzene, 195.0 g (15.4 wt%) of ethylvinylbenzene, 109.6 g (8.6 wt%) of styrene, and 2-phenoxyethylmethacrylic acid were charged. 631.1 g (49.8% by weight) of ester, 865.0 g of toluene, and 35.5 g of boron trifluoride mixed with diethyl ether at 50 ° C The reaction was carried out for 3 hours. After the polymerization solution was stopped with an aqueous solution of sodium hydrogencarbonate, the oil layer was washed three times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried, and weighed to prepare a multifunctional vinyl copolymer PV-B 564 g (yield: 44.5 wt%). The polyfunctional vinyl copolymer PV-B has a Mw of 8,000, a structural unit (a1) containing a vinyl group derived from a divinyl compound, and a molar fraction of 0.34, and a 2-phenoxyethylmethyl group derived from a terminal. The double bond (a2) of the acrylate was 0.03, and the molar fraction (a3) of the combination of the two was 0.37.

Synthesis Example 3 (Polyfunctional Vinyl Copolymer PV-C)

In a 30 L reactor, 4230 g (58.6 wt%) of divinylbenzene, 169 g (2.3 wt%) of ethylvinylbenzene, 1170 g (16.2 wt%) of styrene, and 1649 g (22.8 wt%) of 2,6-xylenol were charged. There were 158 g of ethyl acetate and 12745 g of toluene, and 18 g (120 mmol) of a boron trifluoride complex of boron trifluoride was added at 70 ° C to carry out a reaction for 2 hours. After the polymerization solution was stopped at 53.3 g of 1-butanol, the reaction mixture was poured into a large amount of n-hexane at room temperature to precipitate a polyfunctional vinyl copolymer. The obtained copolymer was washed with n-hexane, filtered, dried, and weighed to prepare a multifunctional vinyl copolymer PV-C 3948 g (yield: 70.9 wt%).

The obtained polyfunctional vinyl copolymer PV-C had an Mn of 2820, a Mw of 10,800 and a Mw/Mn of 3.84. Elemental analysis results were performed, C: 88.2%, H: 7.9 wt%, and O: 3.3 wt%. Elemental analysis results and standards The amount of introduction of the phenolic hydroxyl group of the soluble polyfunctional vinyl aromatic polymer determined by the number average molecular weight in terms of polystyrene was 5.8 (number per molecule). Further, the structural unit containing divinylbenzene was 79.2 mol% and the total structural unit derived from styrene and ethylbenzene was 20.7 mol%. The moiety fraction of the structural unit (a1) containing the vinyl group derived from the 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 it was confirmed that no gel was formed.

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 added, and the mixture was stirred under heating at 120 to 125 ° C for 2 hours, and then at 60 to 62 ° C. The mixture was heated and stirred for 8 hours to obtain an alkali-soluble resin solution AD-A containing a carboxyl group-containing copolymer resin. The solid content of the obtained resin solution was 56.5 wt%, and the acid value (solid content conversion) was 90.3 mgKOH/g, and the area ratio of the carboxyl group-containing copolymer in the resin solution by GPC analysis was 90%, and the weight average molecular weight was 15,000. .

Synthesis Example 5 (alkali soluble resin solution AD-B)

In a 300 ml four-necked flask equipped with a reflux cooler, 96.0 g of FHPA solution, 10.8 g of BPDA, 5.6 g of THPA, and 1.64 g of PGMEA were added. 0.15 g of TEABr was stirred under heating at 120 to 125 ° C for 2 hours, and then 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 copolymerized resin. The solid content of the obtained resin solution was 56.5 wt%, and the acid value (solid content conversion) was 88.1 mgKOH/g, and the area % of the carboxyl group-containing copolymer in the resin solution by GPC analysis was 96%, and Mw was 5400.

Synthesis Example 6 (alkali soluble resin solution AD-C)

In ethyl carbitol acetate, the epoxy equivalent is 220, and the epoxy group of the cresol novolac type epoxy resin having an average of 7 phenol residues in one molecule and an epoxy group in an epoxy group In the case of Mohr, acrylic acid was reacted at a ratio of 1 mol to react THPA at a ratio of 0.6 mol to obtain an alkali-soluble resin solution AD-C containing a carboxyl group-containing copolymer resin. The solid content of the obtained resin solution was 66.7 wt% of a viscous liquid, and the acid value of the resin component was 88 mgKOH/g.

Synthesis Example 7 (Vinyl anisole compound: for comparison)

92 g of bisphenol A and 45 g of potassium hydroxide were dissolved in 200 g of dimethyl hydrazine and 30 g of water, and chloromethylbenzene was dissolved in 100 g of dimethyl hydrazine by dropwise addition at 70 ° C for 1 hour. After 124 g of ethylene and 0.1 g of hydroquinone, the reaction was further continued at 70 ° C for 2 hours. Then, excess water is added to the system and extracted with benzene. The benzene layer is dissolved in sodium hydroxide The liquid and distilled water are washed, neutralized, and dried. After distilling off benzene, it was recrystallized from ethanol (yield 90%), and a vinylanisole compound (VB) represented by the following formula (3) was obtained.

Example 1 (modulation of resin composition)

The alkali-soluble resin solution AD-A obtained in the above Synthesis Example 4 was used as a polyfunctional vinyl copolymer as a polyfunctional vinyl copolymer in an amount of 55 parts by weight in terms of a resin component and 10 parts by weight of trimethylolpropane triacrylate (TMPTA) as an unsaturated compound. Synthetic Example 1 Polyfunctional Vinyl Copolymer PV-A 7 parts by weight, 2-methyl-1-[4-(methylsulfonyl)phenyl]-2-morpholinylpropane as a photopolymerization initiator 2-ketone (initiator A) 2 parts by weight, epoxy resin (Epotot YD-134, manufactured by Nippon Steel Chemical Co., Ltd.), 26 parts by weight, sensitizer (EABF, manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.04 by weight and acetic acid The ester was mixed in 100 parts by weight, and dissolved in a stirrer for 1 hour to prepare a resin composition solution, and a photosensitive resin composition was prepared.

(dry film resisting agent)

The resin composition solution prepared as described above is applied onto a polyester film having a thickness of 25 μm and a width of 600 mm by a die coater at 80 to 120 ° C. The drying was carried out in a continuous four-stage drying oven set in a temperature range to obtain an insulating resin layer having a residual solvent ratio of 2.3% and a film thickness of 30 μm. A polyethylene protective film having a thickness of 60 μm was laminated on the dried coating film to prepare a dry film resist.

(Manufacture of multilayer printed wiring board)

After blackening the conductor pattern pattern on a commercially available glass epoxy substrate having a thickness of 0.8 mm, the protective film was peeled off from the dry film resist, and the transfer pressure was 3 kgf/cm ² at 80 ° C. After laminating at a printing speed of 25 cm/min, the polyester film was peeled off after cooling, and a photosensitive resin layer having a thickness of 30 μm was formed on the conductor pattern. Next, on the photosensitive resin layer of the above-mentioned panel, an ultra-high pressure mercury lamp (made by Hitech, illuminance: 11 mJ/cm ² , I-line reference), 250 mJ/cm ^{2 was used} via a negative-type photomask provided with a through-hole pattern. After the exposure was carried out by irradiation with ultraviolet rays, a 1.2% hydrogenated tetramethylammonium solution was used as a developing solution, and after developing at 28 ° C until the conductor circuit pattern was exposed, development was performed for 1 minute, and then pure at a pressure of 3.0 kg/cm ² . The water was washed for 30 seconds to form a through hole having a diameter of 30 μm. Then, it was thermally hardened in an air atmosphere at 180 ° C for 60 minutes to obtain an insulating film.

(Step of roughening the insulating film)

The surface of the obtained insulating film was polished to a thickness of 3 g/cm ² with a sandpaper of #1000, and then impregnated with a liquid temperature of 70 ° C of a 50% aqueous solution of DI-464 based on the slag removal process of the 荏原电产. After the surface was swollen, it was directly washed with water for 1 minute, and then in a water bath at 50 ° C for 2 minutes, and then a potassium permanganate-based roughening liquid PM-465A (50 g/l), PM-465B (15) was used. The liquid was immersed for 5 minutes at a liquid temperature of 60 ° C to roughen the surface. Then, after washing with water for 1 minute, in order to remove the residue of the potassium permanganate solution on the surface, the N-466 neutralizing solution was used, and it was treated at room temperature for 5 minutes. Further, after washing for 1 minute, the mixture was washed by an ultrasonic cleaner for 10 minutes, and dried at 80 ° C for 1 hour to form a fixed portion in which the surface of the insulating layer was roughened.

(plating step of rough surface)

Next, the substrate is subjected to electroless copper plating by the OPC process of Okuno Pharmaceutical Co., Ltd., and then electroplated at a current density of 2 to 2.5 A/dm ² in the Pyrrobrite Process of Shangcun Industrial Co., Ltd. to form no needle. The hole was subjected to precipitation plating at a thickness of 18 μm, and further heat-treated at 110 ° C for 60 minutes, and heat-treated at 180 ° C for 60 minutes to form an insulating film having a copper foil conductor layer formed thereon.

(pattern forming step of the conductor layer)

Then, by forming a well-known etching resist on the formed conductor, unnecessary copper is removed, and the resist is dissolved to obtain a multilayer printed wiring board having plated through holes.

Thereafter, the evaluation of the dry film and the multilayer printed wiring board prepared as described above was carried out as follows.

Further, the physical properties of the insulating film were obtained by vapor-depositing aluminum-deposited aluminum on a commercially available 4 Å wafer, and the laminate of the peeling protective film was subjected to a transfer pressure of 3 kgf/cm ² at 80 ° C. After laminating at a transfer speed of 25 cm/min, the polyester film was peeled off after cooling, and an insulating layer having a thickness of 30 μm was formed on the aluminum vapor-deposited wafer. Next, on the insulating layer of the wafer, a negative-type photomask provided with a test piece pattern, an ultrahigh pressure mercury lamp (manufactured by Hitech, illuminance: 11 mJ/cm ² , I-line reference), and a condition of 250 mJ/cm ² were used. After exposure by ultraviolet irradiation, a 1.2% hydrogenated tetramethylammonium solution was used as a developing solution, and after shaking at 28 ° C until the aluminum vapor deposited wafer was exposed for development for 1 minute, pure water was applied at a pressure of 3.0 kg/cm ² . Washed for 30 seconds to form various test pieces. Then, it was thermally hardened in an air atmosphere at 180 ° C for 90 minutes to obtain a hardened insulating film. The obtained test piece was used for various physical property measurements.

[wrinkle]

The degree of attachment to the finger on the surface of the dried coating film which was lightly pressed by the finger was evaluated by the following criteria.

A: No attachments at all

B: Almost no attachment

C: Slightly attached

X: There is a attached situation

[Sensitivity]

After the above-mentioned dry film was subjected to a blackening treatment of a copper foil, a trapezoidal plate for sensitivity measurement (Kodak 21) was placed, and an ultrahigh pressure mercury lamp (manufactured by Hitech Co., Ltd., illuminance of 11 mJ/cm ² , I-line) was used. After exposure to ultraviolet light irradiation, a condition of 250 mJ/cm ² was used, and a 1.2% hydrogenated tetramethylammonium solution was used as a developing solution, and after shaking at 28 ° C until the aluminum vapor deposited wafer was exposed, development was performed for 1 minute, and then 3.0 kg was applied. The pressure of /cm ² was washed with pure water for 30 seconds, and the portion of the exposed portion was not removed by the number (segment number) (the larger the number of segments, the better the photosensitive property), and the sensitivity was expressed by the number obtained. .

[Glass transfer temperature (Tg)]

The hardened insulating film was measured using a dynamic viscoelastic method.

[Dielectric rate, dielectric tangent function (Tanδ)]

An impedance film of HP4291 (manufactured by Agilent Co., Ltd.) was used as a measuring device, and an insulating film which was hardened at 1 GHz was measured.

[Adhesiveness]

A 90-degree peeling test of the copper foil formed on the insulating film was carried out in accordance with JIS-C6481, and the peel strength (kg/cm) was measured.

[moisture resistance]

The substrate on which the copper plating was applied on the cured film was used as a test piece, and the test piece was placed in a pressure cooker apparatus, and placed in an environment of a temperature of 121 ° C, a pressure of 2 atm, and a humidity of 100% for 200 hours, and then visually observed. The state of the interlayer insulating film was evaluated on the basis of the following criteria.

A: Confirm that there is no change at all.

B: A little change

C: There are significant changes

X: The film is expanded and peeled off

[Welding heat resistance (heat resistance)]

A substrate on which copper plating was applied to the cured film was used as a test piece, and after immersing in a solder bath of 260 ° C for 30 seconds based on the test method of JIS-C6481, the peeling test was repeated three times by a tape, by The state of the coating film was visually observed and evaluated on the basis of the following criteria.

A: The film has not changed after repeating 3 times.

B: A slight change after repeated 3 times

C: There are changes after repeating 2 times.

X: The peeler is produced after repeating 1 time.

Examples 2 to 7, Comparative Examples 1 to 3

As shown in Table 1, an alkali-soluble resin component, an unsaturated compound, an epoxy resin, and other resins were blended, and a photosensitive resin composition and a dry film were prepared in the same manner as in Example 1, and various tests were carried out. The results are shown in Table 1. In the table, the component (A), the component (B), and the component (C) correspond to the component (A), the component (B), and the component (C) of the present invention (including a component for comparison and a component). For weight.

[Industry use value]

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in low dielectric constant and low dielectric tangent function, excellent in workability, and which does not impair other development characteristics such as photocurability and developability. The photosensitive resin composition can be provided There is a multilayer printed wiring board in which a cured film obtained by curing the material is used as an interlayer insulating film, or a dry film resist in which a coating film of a photosensitive resin composition is provided. Further, the photosensitive resin composition and the 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 as a printed wiring board by curing.

Claims (5)

An alkali-developable photosensitive resin composition containing the component (A): a copolymerization of a divinyl compound (a) of 20 to 99 mol% and a monovinyl compound (b) of 80 to 1 mol% a copolymer containing a solvent-soluble polyfunctional vinyl copolymer having a structural unit of an unreacted vinyl group represented by the following formula (a1) and having a content of 10 to 90 mol%, which is derived from the divinyl compound (a), (In the formula, R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms) (B) component: a carboxyl group-containing copolymer (b) obtained by reacting a polyol compound with a polyvalent carboxylic acid, and having an acid value of 50 to 200 mgKOH /g alkali-soluble resin component, and (C) component: photosensitive resin composition of a photoinitiator characterized by the total amount of (A) component, (B) component, and (C) component. The compounding amount of the component (A) is 1 to 98.9 wt%, the compounding amount of the component (B) is 98.9 to 1 wt%, and the compounding amount of the component (C) is 0.1 to 10 wt%. The photosensitive resin composition of claim 1, wherein the solvent-soluble polyfunctional vinyl copolymer has phenolic hydroxyl groups at the terminal Base, and its introduction amount is 2.2 / molecule or more. The photosensitive resin composition of the first aspect of the invention, wherein the solvent-soluble polyfunctional vinyl copolymer has an end group containing an unsaturated bond represented by the following formula (a2) at a terminal end, (herein, R ² means a hydrocarbon group having 1 to 18 carbon atoms which may contain a (thio)ether oxygen atom or a sulfur atom, and R ³ means hydrogen or a methyl group). The photosensitive resin composition of claim 1, wherein the carboxyl group-containing copolymer (b) is a carboxyl group-containing copolymer obtained by reacting a polyol compound having one or more vinyl groups with a polyvalent carboxylic acid, and has a weight average The molecular weight is 3,000 to 40,000, and the acid value is 50 to 200 mgKOH/g. A dry film resist which is a dry film resist provided with a photosensitive resin layer on a peelable supporting substrate, characterized in that the photosensitive resin layer is any one of the first to fourth aspects of the patent application. The photosensitive resin composition is composed of.