JP2007178937A - Photosensitive resin composition and cured object of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in tackiness, photosensitivity and adhesion, capable of forming a pattern by development with an alkaline aqueous solution, and having superior properties in relation to storage stability and thermal stability. <P>SOLUTION: The photosensitive resin composition comprises an epoxy resin, having a skeleton in which bisphenols and biphenols link together through a group represented by Formula (1) and a compound, having an ethylenically unsaturated group in a molecule. The composition comprises a resin (A) soluble in an alkaline aqueous solution, a crosslinking agent (B), a photopolymerization initiator (C) and the epoxy resin as a curing agent (D). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition using an epoxy resin having a bisphenol skeleton and a biphenol skeleton as a curing agent, and a cured product thereof. More specifically, it is useful as a solder resist for printed wiring boards, interlayer insulation materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, dry film resists, plating resists, photosensitive optical waveguides, etc., thermal stability and storage The present invention relates to a liquid and dry film type resin composition excellent in stability and a cured product thereof.

  A photosensitive resin composition using a photosensitive epoxycarboxylate compound has an excellent balance of various properties such as environmental, thermal, and mechanical properties and adhesion to a substrate. For this reason, it has been used for a long time in the fields of paints, coatings, adhesives and the like. Recently, it is well known that it is used in a wide range of industrial fields, such as electrical / electronic component manufacturing applications and printed circuit board manufacturing applications, and its application range is expanding. However, with the expansion of this application field, it has become necessary to add high functions such as heat resistance and adhesion to photosensitive resin compositions using epoxycarboxylate compounds. Development of various photosensitive resin compositions has been actively promoted mainly for substrate production.

  With the aim of reducing the size and weight of portable devices and improving the communication speed, printed circuit boards are required to have high precision and high density. As a result, the requirements for solder resists are becoming increasingly sophisticated, and even more heat-resistant than conventional requirements. Performance that can withstand substrate adhesion, high insulating properties, and electroless gold plating properties while maintaining stability and thermal stability is required, and currently available solder resists cannot sufficiently meet these requirements. For example, Patent Document 1 discloses a solder mask composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy resin and an unsaturated monobasic acid, a photopolymerization initiator, a crosslinking agent, and an epoxy resin. Are listed. However, sufficient heat resistance, adhesion and plating resistance cannot be obtained with the cured product of this composition. Patent Document 2 describes a photopolymerizable resin composition containing a urethane-modified vinyl ester resin. However, with the cured product of this composition, flexibility is obtained, but sufficient heat resistance and adhesion cannot be obtained. Patent Document 3 describes that it is also possible to use a hardly soluble fine particle epoxy as a curing agent and to replace a part thereof with a soluble resin such as a bisphenol F type epoxy resin. Patent Document 4 exemplifies a bisphenol F type epoxy resin as a soluble epoxy resin.

Bisphenol F-type epoxy resin is very effective as a material capable of improving flexibility, adhesion, etc., but has high solubility in a solvent and easily reacts with a photosensitive resin modified with an acid. As a result, there is a drawback that a residue remains during development after pre-baking. Patent Document 5 describes a 4,4′-bisphenol F-type crystalline epoxy resin, and the crystalline resin obtained has a bisphenol-type epoxy resin substantially having a melting point of 50 to 70 ° C. In addition, since the melting point is low, it reacts with the photosensitive resin modified with acid during pre-baking, and there is a disadvantage that a residue remains during development.
Thus, although the bisphenol F-type epoxy resin has excellent cured properties, it is not satisfactory even when it is a 4,4′-bisphenol F-type epoxy resin having poor thermal stability and particularly high crystallinity. The same applies to the storage stability, and the photosensitive resin composition may be stored for a long period of time, which is difficult to handle and has many industrial problems.

JP-A 61-243869 JP-A-9-52925 Japanese Patent Publication No. 7-17737 JP 2000-109541 A JP-A-8-73563

  With the aim of reducing the size and weight of portable devices and improving the communication speed, printed circuit boards are required to have high precision and high density, and as a result, the demand for solder masks has become increasingly sophisticated and more flexible than conventional requirements. In addition to being required to have adhesive properties, solder heat resistance, electroless gold plating resistance, etc., the composition is required to have high storage stability and thermal stability. However, currently available solder masks cannot sufficiently meet these requirements. The object of the present invention is to provide a fine image that can correspond to the high functionality of today's printed wiring boards with excellent photosensitivity to active energy rays, excellent tackiness, adhesion, etc., and can be patterned by development with an aqueous alkaline solution. An object of the present invention is to provide a resin composition having very excellent characteristics in storage stability and thermal stability, and a cured product thereof.

  In order to solve the above-mentioned problems, the present inventors have completed the present invention as a result of intensive studies. That is, the present invention

で表される基を介して結合した骨格を有するエポキシ樹脂及び分子中にエチレン性不飽和基を有する化合物を含有することを特徴とする感光性樹脂組成物、
（２）エポキシ樹脂が、下記式（２）

（式中、ｐ、ｑ、ｒ、ｓは繰り返し数を表す。）で表される樹脂を主成分として含有するエポキシ樹脂である、上記（１）に記載の感光性樹脂組成物、
（３）アルカリ水溶液可溶性樹脂（Ａ）、架橋剤（Ｂ）、光重合開始剤（Ｃ）、硬化剤（Ｄ）を含有する感光性樹脂組成物であって、硬化剤（Ｄ）として上記（１）または（２）に記載のエポキシ樹脂を含有することを特徴とする感光性樹脂組成物、
（４）前記式（２）においてくり返し数ｐとｒの総和（ＰＲ）とｑとｓの総和（ＱＳ）が０．５≦ＰＲ/ＱＳ≦５０であるエポキシ樹脂を含有する上記（２）または（３）に記載の感光性樹脂組成物、
（５）ビスフェノール類が４、４’−ビスフェノールＦである上記（１）〜（４）のいずれか一項に記載の感光性樹脂組成物、
（６）エポキシ樹脂が、ビスフェノール類および／またはビフェノール類をグリシジル化して得られるエポキシ樹脂とビスフェノール類および／またはビフェノール類を反応させて得られたものである上記（１）〜（５）のいずれか１項に記載の感光性樹脂組成物、
（７）上記（１）〜（６）に記載の感光性樹脂組成物を表面支持体に塗布して得られるシート状組成物、
（８）上記（１）〜（７）のいずれか一項に記載の感光性樹脂組成物の硬化物、
（９）上記（８）に記載の硬化物の層を有する基材、
（１０）上記（９）に記載の基材を有する物品
に関する。 (1) Bisphenols and biphenols are represented by the formula (1)

A photosensitive resin composition characterized by containing an epoxy resin having a skeleton bonded via a group represented by formula (1) and a compound having an ethylenically unsaturated group in the molecule;
(2) The epoxy resin has the following formula (2)

(Wherein p, q, r and s represent the number of repetitions), the photosensitive resin composition according to (1) above, which is an epoxy resin containing a resin represented by a main component,
(3) A photosensitive resin composition containing an alkaline aqueous solution-soluble resin (A), a crosslinking agent (B), a photopolymerization initiator (C), and a curing agent (D), wherein the curing agent (D) is the above ( 1) or a photosensitive resin composition containing the epoxy resin according to (2),
(4) The above (2) or (2) containing an epoxy resin in which the sum (PR) of the repetition numbers p and r and the sum (QS) of q and s are 0.5 ≦ PR / QS ≦ 50 in the formula (2) The photosensitive resin composition according to (3),
(5) The photosensitive resin composition according to any one of (1) to (4), wherein the bisphenol is 4,4′-bisphenol F,
(6) Any of the above (1) to (5), wherein the epoxy resin is obtained by reacting an epoxy resin obtained by glycidylating bisphenols and / or biphenols with bisphenols and / or biphenols The photosensitive resin composition according to claim 1,
(7) A sheet-like composition obtained by applying the photosensitive resin composition according to (1) to (6) to a surface support,
(8) A cured product of the photosensitive resin composition according to any one of (1) to (7) above,
(9) A substrate having a layer of the cured product according to (8) above,
(10) The present invention relates to an article having the base material described in (9).

  The photosensitive resin composition of the present invention not only has excellent properties as the composition itself and its cured product, but also has performance that is particularly excellent in storage stability and thermal stability.

  The photosensitive resin composition of the present invention contains an epoxy resin having a bisphenol skeleton and a biphenol skeleton and a compound having an ethylenically unsaturated group as one component thereof, and is useful as a high-performance resist or the like with little heat denaturation. It is. The preferable photosensitive resin composition further contains a photopolymerization initiator. The compound having an ethylenically unsaturated group is not particularly limited as long as it has an ethylenically unsaturated group, but an alkaline aqueous solution-soluble resin and a crosslinking agent are preferably used in combination. The photosensitive resin composition can be obtained by uniformly mixing each component by a conventional method. The photosensitive resin composition may contain an inorganic filler or the like as necessary.

で表される基を介して結合した骨格を有するエポキシ樹脂（以下、本発明のエポキシ樹脂という）、アルカリ水溶液可溶性樹脂（Ａ）、架橋剤（Ｂ）及び光重合開始剤（Ｃ）を含有する感光性樹脂組成物である。この場合、これら４者のそれぞれの含有割合は、これらの４者の合計に対して、本発明のエポキシ樹脂を５〜６０重量％、好ましくは５〜４０重量％、より好ましくは１０〜３０重量％、アルカリ水溶液可溶性樹脂（Ａ）３５〜８０重量％、好ましくは４０〜７５重量％、架橋剤（Ｂ）３〜３０重量％、好ましくは５〜２０重量％、光重合開始剤（ｃ）を２〜３０重量％、好ましくは４〜１５重量％の範囲内で、４者の合計が１００重量％になるようにそれぞれを含有する。該組成物は更に無機充填剤、溶剤等を含んでいてもよい。 Particularly preferred photosensitive resin compositions are those in which bisphenols and biphenols are represented by the following formula (1):

An epoxy resin having a skeleton bonded via a group represented by the formula (hereinafter referred to as the epoxy resin of the present invention), an aqueous alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C). It is a photosensitive resin composition. In this case, the content of each of these four components is 5 to 60% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight of the epoxy resin of the present invention based on the total of these four components. %, Alkaline aqueous solution-soluble resin (A) 35-80% by weight, preferably 40-75% by weight, crosslinking agent (B) 3-30% by weight, preferably 5-20% by weight, photopolymerization initiator (c) Each is contained in a range of 2 to 30% by weight, preferably 4 to 15% by weight, so that the total of the four members becomes 100% by weight. The composition may further contain an inorganic filler, a solvent and the like.

Below, the photosensitive resin composition of this invention is demonstrated.
Although it does not specifically limit as a compound which has an ethylenically unsaturated group, The compound which has a (meth) acryl group (it means an acryl group or a methacryl group) is preferable. These compounds are disclosed in JP-A No. 2004-155916 and the like as alkaline aqueous solution-soluble resins and crosslinking agents, and are known.

  Below, each component of said component (A)-(D) contained in the preferable aspect of the photosensitive resin composition is demonstrated concretely.

Alkaline aqueous solution-soluble resin (A);
Any resin that can be dissolved and removed with an aqueous alkali solution can be used without particular limitation, and any conventionally known aqueous alkali-soluble resin can be used. For example, an epoxy carboxylate compound obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule may be polybasic. Reaction products obtained by reacting the acid anhydride (c) (alkali aqueous solution-soluble resin having a carboxyl group) and the like (Example 1), and an epoxy compound (d) having two epoxy groups in the molecule and the molecule An epoxycarboxylate compound obtained by reacting with a monocarboxylic acid compound (b) having an ethylenically unsaturated group, a diisocyanate compound (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, Examples thereof include an arbitrary diol compound (g) and a reaction product with an arbitrary acid anhydride (Example 2).

Specifically, for example, the components (a) to (c) used in (Example 1) are preferably the following compound groups.
The epoxy compound (a) having two or more epoxy groups in the molecule used for producing the alkaline aqueous solution-soluble resin (A) of the present invention is particularly an epoxy compound (a) having an epoxy equivalent of 100 to 900 g / equivalent. It is desirable that When the epoxy equivalent is less than 100, the molecular weight of the resulting aqueous alkali-soluble resin (A) may be small and film formation may be difficult or flexibility may not be obtained sufficiently. When the epoxy equivalent exceeds 900, ethylene The introduction rate of the monocarboxylic acid compound (b) having a polymerizable unsaturated group may be low and the photosensitivity may be lowered.

  Specific examples of the epoxy compound (a) having two or more epoxy groups in the molecule include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, Examples thereof include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol-A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, glyoxal type epoxy resin, and heterocyclic epoxy resin.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Company), Epicoat 154 (made by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicoat E1032H60 (oilized shell epoxy) Etc.). Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

  Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.), etc. Examples thereof include bisphenol-F type epoxy resin.

  Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000-H (Nippon Kayaku Co., Ltd.), and bixylenol of YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.). Type epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolak type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.) and Epicoat E157S75 (manufactured by Yuka Shell Epoxy Co., Ltd.).

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

  Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for producing the alkaline aqueous solution-soluble resin (A) include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or Examples include a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and (meth) acrylate derivatives having one hydroxyl group in one molecule. And half-esters that are equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate derivatives, and the like, and photosensitive resin compositions (Meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is particularly preferable.

  As the polybasic acid anhydride (c) used for producing the alkaline aqueous solution-soluble resin (A), any polybasic acid anhydride (c) having at least one acid anhydride structure in the molecule can be used. Acid, acetic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) Monoacetate, 1,2,3,4, -butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone Tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether Lacarboxylic acid dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5 -Dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)- Polybasic acid anhydrides selected from naphtho [1,2-c] furan-1,3-dione are particularly preferred.

For example, the components (d) to (f) used in (Example 2) are preferably the following compound groups. The component (b) in (Example 2) includes the component (b) and the component (c) includes the component (c) and the like.
In order to produce the alkaline aqueous solution-soluble resin (A), the epoxy compound (d) having two epoxy groups in the molecule is preferably an epoxy compound (d) having an epoxy equivalent of 100 to 900 g / equivalent. . When the epoxy equivalent is less than 100 g / equivalent, the molecular weight of the resulting alkaline aqueous solution-soluble resin (A) may be small and film formation may be difficult or flexibility may not be obtained sufficiently. When exceeding, the introduction rate of the monocarboxylic acid compound (b) having an ethylenically unsaturated group is lowered, and the photosensitivity may be lowered.

  The epoxy compound (d) having two epoxy groups in the molecule is not particularly limited as long as it is a compound known as a bifunctional epoxy compound, and is substantially composed mainly of a bifunctional epoxy compound. A trifunctional or higher functional epoxy compound may be included. Examples of the epoxy compound (d) include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and bisphenol-S type epoxy. Resin, bisphenol type epoxy compound such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenation Bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound, etc. Hydrogenated bisphenol Epoxy compounds, halogenated bisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resin, brominated bisphenol-F type epoxy resin, alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compound, 1,6- Examples include aliphatic diglycidyl ether compounds such as hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, polysulfide diglycidyl ether compounds such as polysulfide diglycidyl ether, and biphenol type epoxy resins. .

  Commercially available products of these epoxy compounds include, for example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, and Epomic R-304 (all Mitsui Chemicals), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide), RE -310S (manufactured by Nippon Kayaku), YD-8125 (manufactured by Tohto Kasei), etc., bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide), YDF-2001, YDF-2004, YDF-8170 (any) Also manufactured by Toto Kasei) Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (both manufactured by Dainippon Ink), hydrogenated bisphenol-A types such as HBPA-DGE (manufactured by Maruzen Petrochemicals), Rica Resin HBE-100 (manufactured by Shin Nippon Chemical) Epoxy resin, brominated bisphenol-A type epoxy resin such as DER-513, DER-514, and DER-542 (all manufactured by Dow Chemical Co.), Celoxide 2021 (manufactured by Daicel), Rica Resin DME-100 (manufactured by Shin Nippon Rika) ), Alicyclic epoxy resins such as EX-216 (manufactured by Nagase Kasei), ED-503 (manufactured by Asahi Denka), Rica Resin W-100 (manufactured by Shin Nippon Rika), EX-212, EX-214, EX-850 ( Aliphatic diglycidyl ether compounds such as Nagase Kasei), FLEP-50, FLEP-60 Both east Thiokol Co.) polysulfide type diglycidyl ether compounds such as biphenol type epoxy compounds such as YX-4000 (manufactured by Japan Epoxy Resins) and the like.

  As the diisocyanate compound (e) used for producing the alkaline aqueous solution-soluble resin (A), any compound having two isocyanate groups in the molecule can be used, and a plurality of diisocyanate compounds can be used at the same time. Can be reacted. Among them, diisocyanate compound (e) particularly excellent in flexibility and the like is phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate. , Isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or norbornane-diisocyanate methyl.

  As the carboxylic acid compound (f) having two hydroxyl groups in the molecule used for producing the alkaline aqueous solution-soluble resin (A), a diol compound having both an alcoholic hydroxyl group or a phenolic hydroxyl group and a carboxyl group in the molecule Any alcoholic hydroxyl group excellent in developability in an aqueous alkali solution is particularly preferable, and examples thereof include diol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid.

  The arbitrary diol compound (g) used for producing the alkaline aqueous solution-soluble resin (A) is an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms. All can be used, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-heptanediol 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1, 2-dimethanol, cyclohexane-1,4-dimethanol, hydroxyl group at the end Butadiene-acrylonitrile copolymer, spiroglycol having a hydroxyl group at the end, dioxane glycol having a hydroxyl group at the end, tricyclodecane-dimethanol having a hydroxyl group at the end, a macromonomer having a hydroxyl group at the end and polystyrene in the side chain And a diol compound such as a macromonomer having a hydroxyl group at the terminal and having a polystyrene-acrylonitrile copolymer in the side chain, or a reaction product of these diol compounds with oxides such as ethylene oxide and propylene oxide.

  As the arbitrary acid anhydride used for producing the alkaline aqueous solution-soluble resin (A), the polybasic acid anhydride (c) may be mentioned.

  In the photosensitive resin composition of the present invention, the content ratio of the aqueous alkali solution-soluble resin (A) is usually 15 to 70% by weight, preferably 20 when the nonvolatile component of the photosensitive resin composition is 100% by weight. ~ 60% by weight.

Below, the specific example of the manufacturing method of alkaline aqueous solution soluble resin (A) is demonstrated.
The alkaline aqueous solution-soluble resin (A) of the present invention is prepared by the epoxy compound (a) having two or more epoxy groups in the molecule and the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. It can be obtained by reacting an epoxy carboxylate compound in which an alcoholic hydroxyl group has been formed by the reaction with the polybasic acid anhydride (c) (hereinafter referred to as the second reaction).

  In addition, the production of the aqueous alkaline solution-soluble resin (A) is made up of the epoxy compound (d) having two epoxy groups in the molecule and the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. Urethane reaction (hereinafter referred to as epoxy carboxylate compound in which alcoholic hydroxyl group is generated by reaction (hereinafter referred to as third reaction), diisocyanate compound (e), and carboxylic acid compound (f) having two hydroxyl groups in the molecule. It can be obtained as a fourth reaction). At this time, the diol compound (g) and an optional acid anhydride can be reacted as optional components.

  The first reaction is a solventless or solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, ethylmethylketone, cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, etc. , Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve Acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glutaric acid dial , Esters such as dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the above-mentioned crosslinking agent (B ) Etc. alone or in a mixed organic solvent.

  The raw material charge ratio in this reaction is preferably 80 to 120 equivalent% of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule with respect to 1 equivalent of the epoxy compound (a). When deviating from this range, gelation may occur during the second reaction, and the thermal stability of the finally obtained alkaline aqueous solution-soluble resin (A) may be lowered.

During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reaction product. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octanoic acid Zirconium etc. are mentioned.
Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-ditertiary butyl-4hydroxytoluene, etc. as a thermal polymerization inhibitor.
The first reaction has an end point when the sample oxidation is 1 mg · KOH / g or less, preferably 0.5 mg · KOH / g or less, with appropriate sampling.

  The second reaction is an esterification reaction in which the polybasic acid anhydride (c) is reacted with the reaction solution after the completion of the first reaction. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the reaction product. The reaction temperature at this time is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

  The third reaction is a solvent-free or solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, ethyl methyl ketone, cyclohexanone, and aromatic carbonization such as benzene, toluene, xylene, tetramethylbenzene. Hydrogens, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl Cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glutaric acid dial , Esters such as dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the above-mentioned crosslinking agent (B ) Etc. alone or in a mixed organic solvent.

  The raw material charge ratio in this reaction is preferably 80 to 120 equivalent% of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule with respect to 1 equivalent of the epoxy compound (d). When deviating from this range, gelation may occur during the second reaction, and the thermal stability of the finally obtained alkaline aqueous solution-soluble resin (A) may be lowered.

During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reaction product. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octanoic acid Zirconium etc. are mentioned.
Further, as thermal polymerization inhibitors, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, diphenylpicrylhydrazine, diphenylamine, 3,5-ditertiary butyl-4hydroxy Toluene or the like is preferably used.
The third reaction has an end point when the sample oxidation is 1 mg · KOH / g or less, preferably 0.5 mg · KOH / g or less, while sampling appropriately.

In the fourth reaction, after completion of the third reaction, a carboxylic acid compound (f) having two hydroxyl groups in the molecule and an arbitrary diol compound (g) are added to the reaction solution, and the dispersion or solution is added. Then, the diisocyanate compound (e) described above is gradually added and reacted to cause urethanization. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the reaction product. The reaction temperature at this time is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.
In this case, a solvent or a thermal polymerization inhibitor as described above may be used.
In the third reaction, the end point is the time when absorption in the vicinity of 2250 cm ⁻¹ in the infrared absorption spectrum of the sample disappears while appropriately sampling.

  In the second reaction, the polybasic acid anhydride (c) is preferably added with a calculated value such that the solid content acid value of the aqueous alkali-soluble resin (A) is 50 to 150 mg · KOH / g. When the acid value of the solid content is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, there is a fear that it remains as a residue or in the worst case, patterning cannot be performed. On the other hand, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high, and the photocured pattern may be peeled off.

  In the fourth reaction, the carboxylic acid compound (f) having two hydroxyl groups in the molecule has a calculated value such that the solid content acid value of the aqueous alkali solution-soluble resin (A) is 50 to 150 mg · KOH / g. The diisocyanate compound (e) is ((number of moles of epoxy carboxylate compound produced by the third reaction + number of moles of compound (f)) + number of moles of arbitrary diol compound (g)) / ( It is preferable to charge so that the ratio of the number of moles of the compound (e) is in the range of 1 to 5. When this value is less than 1, the isocyanate remains at the end of the alkaline aqueous solution-soluble resin (A), which is not preferable because the thermal stability is low and gelation may occur during storage. Moreover, when this value exceeds 5, the molecular weight of alkali aqueous solution soluble resin (A) becomes low, and there exists a possibility that the problem of tack property or the problem of low sensitivity may arise. Further, when the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, there is a fear that it remains as a residue or in the worst case, patterning cannot be performed. On the other hand, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high, and the photocured pattern may be peeled off. Arbitrary polybasic acid anhydride is charged with a calculated value such that the solid content acid value of the finally obtained alkaline aqueous solution-soluble resin (A) falls within the above preferred range. The reaction method is the same as in the second reaction. In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

The alkaline aqueous solution-soluble resin (A) thus obtained can be isolated by removing it with an appropriate method when a solvent is used.
The alkali aqueous solution-soluble resin (A) is usually soluble in an alkaline aqueous solution, but is also soluble in the above-described solvent. When used in a solder resist, a plating resist, etc., it can be developed with a solvent.

Cross-linking agent (B);
Any conventionally known crosslinking agent can be used. Usually, the polyfunctional compound which has an ethylenically unsaturated group is preferable, and the (meth) acrylate which has the said (meth) acryl group and another functional group is preferable. Specific examples of the crosslinking agent (B) used in the photosensitive resin composition of the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono ( (Meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meta ) Acrylates) and polycarboxylic acid anhydrides (eg succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) (Meth) acrylate, tripropy Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and ε-caprolactone adduct of hydroxypenic acid neopenglycol Di (meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meta) ) Acrylate, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (eg, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether And epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid, etc. The addition ratio of these is usually 2 to 2 when the nonvolatile component of the photosensitive resin composition is 100% by weight. 40% by weight, preferably 5 to 30% by weight.

Photopolymerization initiator (C);
Any conventionally known photopolymerization initiator can be used. Examples include benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, etc. Specific examples include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether Benzoins such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone , Acetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tertiary Anthraquinones such as tilanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal Benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethyl) And phosphine oxides such as benzoyl) -phenylphosphine oxide. These addition ratios are usually 1 to 30% by weight, preferably 2 to 25% by weight, when the nonvolatile component of the photosensitive resin composition is 100% by weight.

  These photopolymerization initiators (C) can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N -It can be used in combination with accelerators such as benzoic acid derivatives such as dimethylaminobenzoic acid isoamyl ester. The addition amount of these accelerators is preferably 100% by weight or less with respect to the photopolymerization initiator (C).

  The epoxy resin of this invention contained in the photosensitive resin composition of this invention acts as a hardening | curing agent (D) at the time of thermosetting the photosensitive resin composition after photocuring so that it may mention later. In the epoxy resin of the present invention, bisphenols and biphenols are represented by the following formula (1):

で表される基を介して結合した骨格を有するエポキシ樹脂であり、下記式式（２）

（式中、ｐ、ｑ、ｒ、ｓは繰り返し数を表す。）
で表される樹脂が好ましい。
硬化剤（Ｄ）を使用することで、光硬化後の樹脂硬化物に残存するカルボキシル基と加熱により反応し、さらに強固な薬品耐性を有する硬化物が得られる。

An epoxy resin having a skeleton bonded via a group represented by the following formula (2)

(In the formula, p, q, r, and s represent the number of repetitions.)
The resin represented by is preferable.
By using a hardening | curing agent (D), it reacts with the carboxyl group which remain | survives in the resin hardened | cured material after photocuring by heating, and the hardened | cured material which has further firm chemical resistance is obtained.

  The curing agent (D) is a resinous or crystalline compound. Even if it is resinous, when it is mixed with the composition, crystals are precipitated or the epoxy resin is partially released because it is hardly soluble in other components, so the resulting photosensitive resin composition Is often an epoxy resin-dispersed composition. The epoxy resin of the present invention is preferably crystalline. Moreover, what was prepared on the preferable conditions becomes melting | fusing point 180-250 degreeC. Depending on the conditions, a crystal having two or more kinds of endothermic peaks in DSC (thermal differential analysis) is obtained. The epoxy equivalent is usually 200 to 2000 g / eq. Those prepared under preferred conditions are 200-1000 g / eq. It becomes.

  As addition ratio of a hardening | curing agent (D), 50-200 equivalent% of the equivalent calculated from the solid content acid value and usage-amount of alkali aqueous solution-soluble resin (A) is preferable. If it exceeds 200 equivalent%, the developability of the photosensitive resin composition of the present invention may be remarkably lowered, which is not preferable.

The epoxy resin of the present invention uses bisphenols and biphenols as raw materials.
The bisphenols are not particularly specified as long as they are compounds having two phenols, and are not particularly limited.

（式中Ｘはメチレン基、イソプロピリデン基、ビス（トリフルオロメチル）メチン基、エチリデン基、メチルメチリデン基、ビス（メチリデン）ベンゼン基、ビス（メチリデン）ビフェニル基、酸素原子、硫黄原子、スルホニル基、シクロヘキシリデン基、シクロペンチリデン基等を表す。）に示すようなビスフェノール類が挙げられ、具体的にはビスフェノール類としてはビスフェノールＡ、ビスフェノールＦ，ビスフェノールＺ、ビスフェノールＳ、等のビスフェノール類が挙げられる。本発明においては特にその二つのフェノール骨格が、フェノール性水酸基に対しパラ位に結合したもの、例えばビスフェノールＦとしては４，４’−ビスフェノールＦの使用が好ましい。４，４’−ビスフェノールＦは市販品が購入でき、商品名としてはｐ，ｐ’−ＢＰＦ（本州化学株式会社製；４，４’−ビスフェノールＦの化合物の純度＞９９％）が挙げられる。

Wherein X is a methylene group, isopropylidene group, bis (trifluoromethyl) methine group, ethylidene group, methylmethylidene group, bis (methylidene) benzene group, bis (methylidene) biphenyl group, oxygen atom, sulfur atom, sulfonyl group, And bisphenols such as bisphenol A, bisphenol F, bisphenol Z, bisphenol S and the like. Specific examples of the bisphenol include bisphenols such as cyclohexylidene group and cyclopentylidene group. It is done. In the present invention, it is particularly preferable to use 4,4′-bisphenol F as a compound in which the two phenol skeletons are bonded to the phenolic hydroxyl group in the para position, for example, bisphenol F. Commercially available 4,4′-bisphenol F can be purchased, and the product name includes p, p′-BPF (manufactured by Honshu Chemical Co., Ltd .; purity of 4,4′-bisphenol F compound> 99%).

  Biphenols are not particularly limited, and examples thereof include 4,4'-biphenol and bixylenol, with 4,4'-biphenol being preferred.

  In the epoxy resin of the present invention, the ratio of the bisphenol skeleton and the biphenol skeleton is not particularly limited, but taking the structure of the above formula (2) as an example, in the repetition number p, q, r, s, The sum (PR) and the sum of q and s (QS) are preferably 0.5 ≦ PR / QS ≦ 50, and PR ≧ QS. In particular, when QS is too large, that is, when the biphenols contained in the molecular skeleton exceed twice that of bisphenols, synthesis becomes difficult due to the high crystallinity. When PR / QS exceeds 50, the amount of bisphenols in the skeleton is excessively large, so that the molecules are difficult to be oriented, and particularly when the molecular weight is small, a decrease in physical properties is observed.

  The production method of the epoxy resin of the present invention is roughly classified into a one-step method and a fusion method (also referred to as an advanced method or a two-step method. See, New Epoxy Resins Hiroshi Kakiuchi, pages 24-25 and 30-31). In the present invention, either the one-stage method or the fusion method may be used. However, when the synthesis is carried out by the one-stage method, the reaction by which a by-product is obtained tends to occur. Therefore, the fusion method should be selected. Is preferred. Hereinafter, both will be described in detail.

(One-stage method)
In this method, bisphenols and biphenols are mixed with epihalohydrin and reacted in the presence of an alkali metal hydroxide.

  In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin. In the present invention, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 1.0-5.0 mol normally with respect to 1 mol of total hydroxyl groups of bisphenol and biphenol, Preferably it is 1.5-3.5 mol.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.3-2.5 mol normally with respect to 1 mol of total hydroxyl groups of bisphenol and biphenol, Preferably it is 0.5-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the total hydroxyl group of bisphenols and biphenols.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the total hydroxyl group of bisphenols and biphenols used for epoxidation. It is. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

(Fusion method)
This method is a method of reacting an epoxy resin (hereinafter referred to as a raw material epoxy resin) obtained by glycidylating raw material bisphenols and / or biphenols as described above with bisphenols and / or biphenols. The raw material epoxy resin may be a commercially available compound or may be used after epoxidizing bisphenols and / or biphenols. In the case of synthesis, for example, the following method can be adopted.

  The raw material epoxy resin can be obtained by reacting bisphenols and / or biphenols (hereinafter simply referred to as phenols) with epihalohydrin. As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used, and epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 2.0-20.0 mol normally with respect to 1 mol of total hydroxyl groups of bisphenol and biphenol, Preferably it is 2.5-10.0 mol.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of phenol, Preferably it is 0.95-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenols used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After the completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain a hydroxyl group epoxy resin of phenols. The epoxy resin of this invention can be obtained by making the obtained epoxy resin and phenols react.

  This reaction uses a catalyst if necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7 ;, triphenylphosphine, diphenyl Organic phosphines such as sphin and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. These catalysts are generally used in an amount of usually 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm based on the total weight of the phenols and the raw material epoxy resin, although depending on the type. In this reaction, since the reaction proceeds without adding a catalyst, the catalyst is appropriately used in consideration of the reaction temperature and the amount of the reaction solvent.

In this fusion method, a solvent may or may not be used. When a solvent is used, any solvent can be used as long as it does not affect the reaction. For example, the following solvents can be used.
Polar solvents, ethers; dimethyl sulfoxide, N, N′-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, diglyme, triglyme, propylene glycol monomethyl ether, etc.
Ester-based organic solvents; ethyl acetate, butyl acetate, butyl lactate, γ-butyrolactone, etc.
Ketone organic solvent; aromatic organic solvent such as methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; toluene, xylene, etc. The amount of the solvent used is 0 to 300% by weight based on the total weight of phenols and raw material epoxy resin, Preferably it is 0-100 weight%.

  The reaction temperature and reaction time in the fusion method need to be appropriately selected depending on the amount of solvent used and the type and amount of the catalyst, and cannot be generally specified, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is. In view of productivity, it is preferable that the reaction time is short. The reaction temperature is 0 to 250 ° C, preferably 30 to 200 ° C.

  After completion of the reaction, the epoxy resin solution obtained using a solvent can be applied to the photosensitive resin composition of the present invention by adjusting the concentration of the solution as it is. Moreover, the epoxy resin of this invention can also be isolated by removing a catalyst etc. by water washing etc. as needed, and also distilling a solvent off under heating and pressure reduction.

  Moreover, the epoxy resin obtained by the one-step method or the fusion method can be crystallized by crystallization. As a crystallization method, a conventionally known recrystallization method can be applied. Specifically, for example, it is dissolved by heating in an organic solvent such as methyl isobutyl ketone, methyl ethyl ketone, cyclopentane, cooled, and the obtained crystal is filtered and filtered. It can be set as a crystalline epoxy resin by drying.

  In the photosensitive resin composition of this invention, another epoxy resin can also be used together as a hardening | curing agent (D) other than the said epoxy resin. Specific examples include one or more selected from the epoxy compounds (a) and (d) described in the section of the alkali-soluble resin (A). Particularly preferable epoxy resins are crystalline epoxy resins. Those having a softening point or melting point of ℃ or higher are preferred. Specifically, bixylenol-type or biphenol-type crystalline epoxy resins such as YX-4000 manufactured by Japan Epoxy Resin Co., Ltd. and CER-3000 manufactured by Nippon Kayaku Co., Ltd. (both are trade names) or mixtures thereof; Bisphenol S type crystalline epoxy resin; Bisphenol fluorene type crystalline epoxy resin; Hydroquinone type crystalline epoxy resin; Tetrakisphenol ethane type epoxy resin such as GTR-1800 (trade name) manufactured by Nippon Kayaku Co., Ltd .; Nissan Chemical Industries, Ltd. Examples thereof include heterocyclic crystal epoxy resins such as TEPIC (trade name) manufactured by the Company.

The photosensitive resin composition of the present invention further contains various additives as necessary, for example, silica, clay, quartz glass powder, alumina powder, aluminum hydroxide, aluminum oxide, magnesium oxide, aluminum nitride, magnesium hydroxide. , Hydrated alumina, hydrated magnesium, calcium carbonate, magnesium carbonate, barium titanate, silicon carbide, zirconium silicate, calcium silicate, talc, clay, mica, glass fiber powder, etc., preferably inorganic filler And thixotropy imparting agents such as phthalocyanine; colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicone, fluorine leveling agents and antifoaming agents; and polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether. For the purpose of improving performance To it can be.
The amount of the filler used is more preferably the photosensitive resin composition containing the above four (epoxy resin of the present invention, alkaline aqueous solution-soluble resin (A), crosslinking agent (B), photopolymerization initiator (C)). It is 0-100 weight% with respect to the sum total of these 4 persons, Preferably it is about 0-60 weight%.

The photosensitive resin composition of the present invention may contain a solvent as necessary. Usable solvents include, for example, ketones such as acetone, ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dipropylene glycol. Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Examples include esters, cyclic esters such as γ-butyrolactone, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. May be.
In the preferable photosensitive resin composition containing the components (A) to (D), the solvent is used in an amount of 0 to 50% by weight, preferably about 0 to 20% by weight, based on the total of these four components. is there.

In addition, when using the above-mentioned hardening | curing agent (D) as a liquid type resist, it is good also as a photosensitive resin composition of this invention by mixing with another component previously, However, (A) component is the main ingredient. It is preferable to mix and use the mixture and the mixture containing the curing agent (D) as a main component. In addition, when the photosensitive resin composition of the present invention contains an epoxy resin curing accelerator,
Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, and triethanol. Amines, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, tetraphenyl Tetra-substituted phosphonium / tetra-substituted borate such as phosphonium / tetraphenyl borate, tetraphenylphosphonium / ethyl triphenyl borate, 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / Tetraphenyl boron salts such as tiger tetraphenylborate, and melamine can be mentioned.
The curing accelerator is used as necessary in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the nonvolatile content of the photosensitive resin composition. Moreover, in the said preferable embodiment, a hardening accelerator is mixed and used for the mixture which has (A) component as a main ingredient.

  When the photosensitive resin composition of the present invention is used as a dry film type resist, the components (A), (B), (C), (D), fillers, additives and the like are blended to form a photosensitive layer. . The photosensitive layer is sanded with a support layer and a protective layer to form a dry film. When used, the protective layer is peeled off, laminated on the substrate, exposed, and the support layer is peeled off for development.

  The photosensitive resin composition (liquid or film-like) of the present invention not only has excellent sensitivity to active energy rays for fine images that can correspond to the high functionality of a printed wiring board, but also has excellent tackiness and adhesion. The pattern can be formed by development with an aqueous alkali solution, and the cured product is excellent in various properties such as heat resistance, plating resistance, and thermal conductivity. In addition, the photosensitive resin composition of the present invention has very excellent characteristics particularly in its storage stability and thermal stability. In addition to being useful as resist materials for insulating materials between electronic components, optical waveguides connecting optical components, solder resist for printed circuit boards, coverlays, etc., color filters, printing inks, sealants, paints, coating agents It can also be used as an adhesive.

  The photosensitive resin composition of the present invention can be cured by irradiation with energy rays such as ultraviolet rays and by a heating operation. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used. Thereafter, the cured product of the present invention can be obtained by further irradiating with ultraviolet rays as necessary and then heat-treating at a temperature of usually 100 to 20 ° C., preferably 140 to 180 ° C.

  The cured product of the photosensitive resin composition of the present invention is used for, for example, a resist film, an interlayer insulating material for a build-up method, an optical waveguide, a printed wiring board, an electric / electronic / optical substrate such as an optoelectronic substrate or an optical substrate, etc. Is done. Specific articles using these include, for example, computers, home appliances, portable devices, and the like.

Specifically, for example, when producing a printed wiring board using the photosensitive resin composition of the present invention, first, a screen printing method, a spray method, a roll coating method, an electrostatic coating method is applied to the printed wiring board. By applying the photosensitive resin composition of the present invention in a film thickness of 0.5 to 160 μm by a method such as curtain coating, and drying the coating film at 50 to 110 ° C., preferably 60 to 100 ° C., A coating film is formed. Thereafter, the coating film is irradiated directly or indirectly with high energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² directly or indirectly through a photomask having an exposure pattern such as a negative film, and the unexposed portion will be described later. Is developed by spraying, rocking dipping, brushing, scrubbing or the like. Thereafter, if necessary, further ultraviolet irradiation is performed, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., so that the gold plating property is excellent, and heat resistance, solvent resistance, acid resistance, A printed wiring board having a permanent protective film that satisfies various properties such as adhesion and flexibility can be obtained.

  Examples of the alkaline aqueous solution used for development include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline solutions and tetramethylammonium. Examples thereof include organic alkaline aqueous solutions such as hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, unless otherwise specified, “parts” are parts by weight and “%” is% by weight. The softening point and epoxy equivalent were measured under the following conditions.
・ Softening point
It measured by the method described in JIS K-7234.
・ Epoxy equivalent
It is measured by the method described in JIS K-7236, and the unit is g / eq.

Synthesis example 1
EOCN-103S (polyfunctional cresol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy compound (a) having two or more epoxy groups in a molecule in a 3 L flask equipped with a stirrer and a reflux tube: 210.0 g / equivalent) is 860.0 g, 288.3 g of acrylic acid (molecular weight: 72.06) is used as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and carbitol acetate is used as the reaction solvent. Was charged with 4.921 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor and 4.921 g of triphenylphosphine as a reaction catalyst, and the acid value of the reaction solution at a temperature of 98 ° C. Was reacted until 0.5 mg · KOH / g or less, to obtain an epoxycarboxylate compound.
Next, 169.8 g of carbitol acetate as a reaction solvent and 201.6 g of tetrahydrophthalic anhydride as a polybasic acid anhydride (c) were added to this reaction solution, and reacted at 95 ° C. for 4 hours to obtain an aqueous alkali solution-soluble resin (A). A resin solution containing 67% by weight was obtained (this solution is referred to as A-1). When the acid value was measured, it was 69.4 mg · KOH / g (solid content acid value: 103.6 mg · KOH / g).

Synthesis example 2
As an epoxy compound (d) having two epoxy groups in a molecule in a 3 L flask equipped with a stirrer and a reflux tube, Nippon Kayaku RE-310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: (184.0 g / equivalent)) 368.0 g, 141.2 g of acrylic acid (molecular weight: 72.06) as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl as the thermal polymerization inhibitor 1.02 g of ether and 1.53 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mg · KOH / g or less, and an epoxycarboxylate compound (theoretical molecular weight) : 509.2).
Next, 755.5 g of carbitol acetate was used as a reaction solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.2) as a carboxylic acid compound (f) having two hydroxyl groups in the molecule. 16) was added to 268.3 g, 1.08 g of 2-methylhydroquinone as a thermal polymerization inhibitor and 140.3 g of spiroglycol (molecular weight: 304.38) as a diol compound (g), and the temperature was raised to 45 ° C. To this solution, 485.2 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) was gradually added dropwise as a diisocyanate compound (e) so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the temperature was raised to 80 ° C., and the mixture was reacted for 6 hours until absorption near 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method to obtain a resin solution containing 65% by weight of the aqueous alkali-soluble resin (A). (This solution is referred to as A-2). When the acid value was measured, it was 52.0 mg · KOH / g (solid content acid value: 80.0 mg · KOH / g).

Synthesis example 3
While purging a flask equipped with a thermometer, condenser, fractionator, and stirrer with nitrogen purge, 370 parts epichlorohydrin, methanol 26 with respect to 100 parts bisphenol F (trade name p, p'-BPF manufactured by Honshu Chemical Co., Ltd.) Then, 40 parts by weight of flaky sodium hydroxide was added in portions over 100 minutes under reflux conditions. Thereafter, the post reaction was further carried out at 70 ° C. for 1 hour. Subsequently, 150 parts of water was added and washed with water twice, and excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. 312 parts of methyl isobutyl ketone was added to the residue and dissolved, and 10 parts of 30% aqueous sodium hydroxide solution was added at 70 ° C. and reacted for 1 hour. After the reaction, washing with water was performed 3 times to remove the generated salt and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 150 parts of bisphenol F type epoxy resin. The epoxy equivalent of the obtained epoxy resin was a liquid epoxy resin of 163 g / eq. 82 parts of the obtained epoxy resin, 21 parts of 4,4′-biphenol and 30 parts of methyl isobutyl ketone were added, and 0.09 part of triphenylphosphine was added with stirring. After reacting for 10 hours under reflux, the solvent was distilled off under reduced pressure by heating to obtain 102 parts of an epoxy resin (D-1) represented by the formula (2). The epoxy equivalent of the obtained epoxy resin was 421 g / eq. Further, the PR / QS distribution ratio (preparation ratio, the same applies hereinafter) of the formula (2) is PR / QS≈2.2. In the examples, the epoxy resin obtained was powdered in a mortar.

Synthesis example 4
While performing a nitrogen purge on a flask equipped with a thermometer, condenser, fractionator, and stirrer, 80 parts of bisphenol F (trade name p, p′-BPF, manufactured by Honshu Chemical Co., Ltd.) 4,4,4′-biphenol 20 To this part, 370 parts of epichlorohydrin and 26 parts of methanol were added and heated to 65-70 ° C. with stirring. Then, 40 parts of flaky sodium hydroxide was added in portions over 100 minutes under reflux conditions. Thereafter, the post reaction was further carried out at 70 ° C. for 1 hour. Subsequently, 150 parts of water was added and washed with water twice, and excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. To the residue, 460 parts of methyl isobutyl ketone was added and dissolved. At 70 ° C., 10 parts of a 30% aqueous sodium hydroxide solution were added and reacted for 1 hour. After the reaction, washing with water was performed 3 times to remove the generated salt and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 150 parts of bisphenol F type epoxy resin. The epoxy equivalent of the obtained epoxy resin was a liquid epoxy resin of 170 g / eq. 85 parts of the obtained epoxy resin, 21 parts of a compound represented by 4,4′-biphenol, and 30 parts of methyl isobutyl ketone were added, and 0.09 part of triphenylphosphine was added with stirring. After reacting for 10 hours under reflux, 200 parts of methyl isobutyl ketone was added and cooled to 30 ° C. to precipitate crystals. The crystal was filtered and dried to obtain 94 parts of a white powdery crystalline epoxy resin (D-2) of the present invention. The epoxy equivalent of the obtained epoxy resin was 422 g / eq. Since the crystallization was performed, the detailed distribution ratio of PR and QS is unknown, but the charging ratio is PR / QS≈1.2.

Examples 1 and 2 and Comparative Example 1
(A-1) and (A-2) obtained in Synthesis Example 1 and Synthesis Example 2 and curing agent (D-1) obtained in Synthesis Example 3 and a commercially available bisphenol F type epoxy resin as a comparative example. (Japan Epoxy Resin Epicoat 4003P) was mixed at a blending ratio shown in Table 1 (unit is “part”) and kneaded with a three-roll mill to obtain a photosensitive resin composition for comparison with the present invention. This was applied to a printed circuit board by screen printing so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes, 40 minutes, and 50 minutes, respectively. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area. The obtained printed circuit board with a resin layer was washed with water and dried, and then subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a printed circuit board with a cured film.
About the obtained photosensitive resin composition and the printed circuit board with a cured film, the test was done about tack property, thermal stability, photosensitivity, resolution, adhesiveness, and plating resistance as mentioned later. In addition, in the cured physical properties other than the thermal stability, evaluation was performed for a drying time after coating of 30 minutes. The results are shown in Table 2. The test method and evaluation method are as follows.

Tackiness: Absorbent cotton was rubbed onto the dried film applied to the substrate, and the tackiness of the film was evaluated.
○: Absorbent cotton does not stick.
× ··· Absorbent cotton lint sticks to the membrane.

Thermal stability: The developability when the drying time at 80 ° C. was performed for 30, 40 and 50 minutes was evaluated, and the following evaluation criteria were used. At the time of development, the ink was completely removed, and the evaluation was performed based on the time when the development was possible.
○ ・ ・ ・ ・ within 60 seconds
× ... 60 seconds or more

Resolution: A 50 μm negative pattern is brought into intimate contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 300 mJ / cm ² . Next, development is performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern is observed with a microscope. The following criteria were used:
○ The pattern edge is a straight line and is resolved.
X: Peeling or pattern edges are jagged.

Photosensitivity: 21 steps of tablet (manufactured by Kodak Co., Ltd.) are brought into close contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 500 mJ / cm ² . Next, development is performed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of stages of the coating film remaining without development is confirmed.

Adhesiveness: 100 square grids of 1 mm square were formed on the cured layer, and a peeling test using a cellophane adhesive tape was performed, and evaluation was performed based on the number of resists in close contact with the test piece. The following criteria were used to describe the results.
○ ・ ・ ・ ・ 100/100 No abnormality
× ・ ・ ・ ・ ≦ 99/100

Heat resistance: A rosin-based plax was applied to the cured layer and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as 1 cycle and repeated 3 cycles. After cooling to room temperature, a peeling test with a cellophane adhesive tape was performed and evaluated according to the following criteria.
〇 ・ ・ ・ ・ No abnormalities in the appearance of the coating film and no swelling or peeling
× · · · with paint film swelling or peeling

(Gold-proof plating) A printed circuit board with a hardened layer was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, washed with water, and then 14.4 wt% persulfuric acid The test substrate was immersed in an aqueous ammonia solution at room temperature for 3 minutes, then washed with water, and further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water. Next, this substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate Ni— After immersing in 865M 20vol% aqueous solution, pH 4.6) for 20 minutes and performing nickel plating, it was immersed in 10vol% sulfuric acid aqueous solution for 1 minute at room temperature and washed with water. Next, the test substrate was immersed for 10 minutes in a gold plating solution at 95 ° C. (Meltex, aqueous solution of Aurolectroles UP 15 vol% and potassium gold cyanide 3 vol%, pH 6), electroless gold plating was performed, and then washed with water. It was immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. A cellophane adhesive tape was attached to the obtained electroless gold plating evaluation substrate, and the state when peeled off was observed.
○: No abnormality.
X: The one where peeling was seen.

Table 1
Examples Comparative examples
Note 1 2 1
Resin solution A-1 51.80 51.80
A-2 51.80
Cross-linking agent (B)
DPHA * 1 3.38 3.38
HX-220 * 2 3.38
Photopolymerization initiator (C)
Irgacure 907 * 3 4.50 4.50 4.50
DETX-S * 4 0.45 0.45 0.45
Curing agent (D)
D-1 33.46 33.46
Epicoat 4003P * 5 33.46
Curing accelerator Melamine 1.00 1.00 1.00
Filler Barium sulfate 15.15 15.15 15.15
Phthalocyanine green 0.45 0.45 0.45
Additive BYK-354 * 6 0.39 0.39 0.39
KS-66 * 7 0.39 0.39 0.39
Solvent CA * 8 4.87 4.87 4.87

* 1 Nippon Kayaku: Dipentaerythritol polyacrylate * 2 Nippon Kayaku: ε-caprolactone-modified hydroxypivalate neopentyl glycol diacrylate * 3 Vantico: 2-methyl- (4- (methylthio) phenyl)- 2-morpholino-1-propane * 4 Nippon Kayaku: 2,4-diethylthioxanthone * 5 Japan Epoxy Resin: Bisphenol F-type epoxy resin * 6 Big Chemie: Leveling agent * 7 Shin-Etsu Chemical: Antifoaming agent * 8 Carbitol acetate

Table 2
Example 1 2
Comparative Example 1
Evaluation item tackiness ○ ○ ○
Thermal stability 30 minutes ○ ○ ○
40 minutes ○ ○ ×
50 minutes ○ ○ ×
Developability ○ ○ ×
Resolution ○ ○ ×
Light sensitivity 11 8 5
Adhesiveness ○ ○ ×
Heat resistance ○ ○ ×
Gold plating resistance ○ ○ ○

Example 3 and Comparative Example 2: Preparation of Dry Film A photosensitive resin composition as Example 3 was obtained in the same manner as in Synthesis Example 2 except that carbitol acetate was changed to propylene glycol monomethyl ether in Synthesis Example 2. 54.44 g of the resulting resin solution, 3.54 g of HX-220 (trade name: manufactured by Nippon Kayaku Co., Ltd., diacrylate monomer) as a crosslinking agent (B), and Irgacure 907 (as a photopolymerization initiator (C)) Ciba Specialty Chemicals) (4.72 g) and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) (0.47 g), (D-2) obtained in Synthesis Example 4 as a curing agent component, 14.83 g, Add 1.05 g of melamine as a curing accelerator and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent, knead with a bead mill, and uniformly disperse. To obtain a photosensitive resin composition.
As the photosensitive resin composition as Comparative Example 2, 54.44 g of the same resin solution as in Example 3, and HX-220 (trade name: Nippon Kayaku Co., Ltd. diacrylate monomer) 3 as the crosslinking agent (B) 3 .54g, 4.72g of Irgacure 907 (Ciba Specialty Chemicals) as the photopolymerization initiator (C) and 0.47g of Kayacure DETX-S (Nippon Kayaku Co., Ltd.), and Japan Epoxy as the curing agent component 14.83 g of resin Epicoat 4003P, 1.05 g of melamine as a curing accelerator and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent were kneaded in a bead mill and uniformly dispersed to obtain a comparative photosensitive resin composition. .
The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. A polyethylene film serving as a protective film was attached to each other to obtain a dry film 1 (Example 3) and a dry film 2 (Comparative Example 2).
The obtained dry film was allowed to stand at room temperature for 1 week, and its storage stability was compared. The comparison was made with the developability immediately after the creation of the dry film and one week later. The evaluation criteria were ◯ when the ink was completely removed during development and the development time was within 60 seconds, and x when it exceeded 60 seconds. The results are shown in Table 3 below.
In addition, the following operation was performed as a method of obtaining the hardened | cured material at the time of evaluating.
The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area.

Table 3
Example 3
Comparative Example 2
Dry film Immediately after creation One week later Immediately after creation One week later Development performance ○ ○ ○ ×

  From the above results, the photosensitive resin composition and the cured product of the present invention have no tackiness and high sensitivity, and the cured film has not only excellent heat resistance and gold plating resistance, but also the composition. It is clear that it has very excellent characteristics in terms of storage stability and thermal stability.

Claims (10)

Bisphenols and biphenols are represented by the formula (1)

A photosensitive resin composition comprising an epoxy resin having a skeleton bonded via a group represented by formula (1) and a compound having an ethylenically unsaturated group in the molecule. The epoxy resin has the following formula (2)

The photosensitive resin composition of Claim 1 which is an epoxy resin which contains as a main component the resin represented by (In formula, p, q, r, s represents a repeating number.). A photosensitive resin composition comprising an aqueous alkali-soluble resin (A), a crosslinking agent (B), a photopolymerization initiator (C), and a curing agent (D), wherein the curing agent (D) is used as a curing agent (D). The photosensitive resin composition characterized by including the epoxy resin of description. 4. The epoxy resin according to claim 2, which contains an epoxy resin in which the sum (PR) of repetition numbers p and r and the sum (QS) of q and s are 0.5 ≦ PR / QS ≦ 50 in the formula (2). Photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 4, wherein the bisphenol is 4,4'-bisphenol F. The epoxy resin is obtained by reacting an epoxy resin obtained by glycidylation of bisphenols and / or biphenols with bisphenols and / or biphenols, according to any one of claims 1 to 5. Photosensitive resin composition. The sheet-like composition obtained by apply | coating the photosensitive resin composition as described in any one of Claims 1-6 to a surface support body. Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-7. The base material which has the layer of the hardened | cured material of Claim 8. An article comprising the substrate according to claim 9.