JP4501056B2 - Epoxy acrylate resin, curable resin composition, alkali-developable photosensitive resin composition, and cured products thereof - Google Patents

Description

The present invention relates to a novel epoxy acrylate resin and curable resin composition, and an alkali development type photosensitive resin composition. More specifically, it is suitable for the production of printed circuit boards, especially flexible printed circuit boards, such as permanent protective films such as overcoats, undercoats and insulation coats for printed circuit boards, solder resist inks, interlayer insulation materials for build-up substrates, etc. The present invention relates to a curable resin composition suitable for a solder resist ink that can be developed with a dilute alkaline solution.

  Recent progress in printed wiring boards has been remarkable, especially with the improvement of surface mounting technology, the integration of printed wiring boards has been accelerated, and in addition to high density and high reliability, it has both mass productivity and economy. There is a need for a method for forming a resist pattern. For this reason, the demand for higher density of solder resist ink is more severe, and the conventional resist pattern forming method for printed wiring boards by screen printing has a low resolution, which makes it impossible to meet this requirement. Alkali developable solder resist inks that can be used for photographic development utilizing high photographic methods have been used.

  In recent years, flexible printed wiring boards have been widely used. As a result, they are flexible enough to be applied to flexible printed wiring boards, and can be used for high resolution photo development. The demand for a new solder resist ink is increasing. As a solder resist ink having flexibility and capable of alkali development, which can be applied to such applications, conventionally, for example, acrylic acid is reacted with a bisphenol type epoxy resin, and then the hydroxyl group generated by the reaction is changed. An acid pendant epoxy vinyl ester resin obtained by reacting an acid anhydride is used as a main agent, and a diluent, a photopolymerization initiator, and an epoxy resin are blended with this resin (see, for example, Patent Document 1). ). However, a solder resist ink using an acid pendant type epoxy vinyl ester resin derived from the above bisphenol type epoxy resin as a main agent is a substrate for flexible printed wiring board applications, although the cured product itself has flexibility. The adhesion to the substrate film is poor, and as a result, the flexibility of the printed wiring board itself is still not sufficient, and the heat resistance of the cured product is further inferior, and the heat resistance of the printed wiring board is also inferior. It had a problem.

JP 05-43654 A (page 2-5)

  The problem to be solved by the present invention is remarkably excellent in flexibility and heat resistance, and particularly excellent in adhesion to a substrate film in a flexible printed wiring board application, and has both excellent flexibility and solder heat resistance. Provided are a photocurable resin composition that can be used as a flexible printed wiring board, an epoxy acrylate resin suitable for a flexible solder resist ink, a curable resin composition containing the same, an alkali development type photosensitive resin composition, and a cured product thereof. There is to do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors converted glycidyl into a modified polyphenol (A) obtained by acetalizing a polyphenol (a1) and a polyvalent vinyl ether (a2). The epoxy acrylate resin derived from the etherified epoxy resin (B) is a novel compound, and by using this compound, a diluent, a photopolymerization initiator, an epoxy resin, and the like are blended into the flexible resin. The inventors have found that the adhesion and solder heat resistance can be improved, and have completed the present invention.

  That is, the present invention provides an epoxy resin (B) obtained by glycidyl etherification of a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2). An epoxy acrylate resin obtained by reacting an ethylenically unsaturated monobasic acid and an epoxy acrylate resin reacted with a polybasic acid compound are provided.

  The present invention also provides an epoxy resin (B) obtained by glycidyl etherification of a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2). An epoxy acrylate resin obtained by reacting an ethylenically unsaturated monobasic acid, a curable resin composition containing an optical or thermal polymerization initiator as essential components, and further containing an epoxy resin Provided are an alkali development type photosensitive resin composition and a cured product obtained by curing the composition.

  According to the present invention, a cured product that is remarkably excellent in flexibility and heat resistance can be obtained, and in particular, when used as a flexible solder resist ink, formation of a resist pattern excellent in flexibility, adhesion, and solder heat resistance. It is possible to obtain a flexible printed wiring board that can be developed with a dilute alkaline aqueous solution.

  The epoxy acrylate resin (C) of the present invention is an epoxy formed by glycidyl etherification of a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2). The epoxy resin (B) can be obtained by reacting the resin (B) with an ethylenically unsaturated monobasic acid. The epoxy resin (B) comprises an aromatic hydroxyl group and a polyvalent vinyl ether (a2) of the polyhydric phenol (a1). It has a chemical structure in which polyhydric phenols are subjected to addition reaction to extend the molecular chain by acetal group bonding, and the hydroxyl group of the resulting modified polyphenols (A) is glycidyl etherified by epihalohydrin. Is. The acetalization reaction here refers to the chemical reaction formula (1)

で表される反応であり，芳香族性水酸基とビニルエーテル基が付加反応して生成したアセタール基を介して結合する化学反応を示す。

A chemical reaction in which an aromatic hydroxyl group and a vinyl ether group are bonded via an acetal group formed by an addition reaction.

  The polyhydric phenols (a1) are not particularly limited as long as they are aromatic compounds containing more than one aromatic hydroxyl group in one molecule. For example, hydroquinone, resorcin, catechol, those Dihydroxybenzenes such as substituent-containing compounds; 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6- Dihydroxynaphthalenes such as dihydroxynaphthalene and substituents thereof; bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2- Bis (3-methyl-4-hydroxyphenyl) propane (bis Enol C), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), bis (4-hydroxyphenyl) sulfone (Bisphenol S) and bisphenols such as those containing substituents;

Bisnaphthols such as bis (2-hydroxy-1-naphthyl) methane and bis (2-hydroxy-1-naphthyl) propane, phenol / formaldehyde polycondensate, orthocresol / formaldehyde polycondensate, 1-naphthol / formaldehyde heavy Condensate, 2-naphthol / formaldehyde polycondensate, phenol / acetaldehyde polycondensate, orthocresol / acetaldehyde polycondensate, 1-naphthol / acetaldehyde polycondensate, 2-naphthol / acetaldehyde polycondensate, phenol / salicylaldehyde polycondensate Condensates, orthocresol / salicylaldehyde polycondensates, 1-naphthol / salicylaldehyde polycondensates, 2-naphthol / salicylaldehyde polycondensates and the like, and compounds containing substituents on these aromatic rings;

Phenol / dicyclopentadiene polyadduct, phenol / tetrahydroindene polyadduct, phenol / 4-vinylcyclohexene polyadduct, phenol / 5-vinyl noborna-2-ene polyadduct, phenol / α-pinene polyadduct, phenol / Β-pinene polyadduct, phenol / limonene polyadduct, orthocresol / dicyclopentadiene polyadduct, orthocresol / tetrahydroindene polyadduct, orthocresol / 4-vinylcyclohexene polyadduct, orthocresol / 5- Vinyl noborna-2-ene polyadduct, orthocresol / α-pinene polyadduct, 1-naphthol / dicyclopentadiene polyadduct, 1-naphthol / 4-vinylcyclohexene polyadduct, 1-naphthol / 5-vinyl norbornadiene Polyadduct, 1- Phthol / α-pinene polyadduct, 1-naphthol / β-pinene polyadduct, 1-naphthol / limonene polyadduct, orthocresol / β-pinene polyadduct, orthocresol / limonene polyadduct, etc. Phenols (naphthols) / dienes polyadducts such as substituent-containing compounds, phenol / p-xylene dichloride polycondensates, 1-naphthol / p-xylene dichloride polycondensates, 2-naphthol / p-xylene dichloride Polycondensates, phenol / bischloromethylbiphenyl polycondensates, orthocresol / bischloromethylbiphenyl polycondensates, 1-naphthol / bischloromethylbiphenyl polycondensates, 2-naphthol / bischloromethylbiphenyl polycondensates and these Condensation with phenols / aralkyl resins such as those containing substituents Kind, and the like.

  Examples of substituents in these substituent-containing products include alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, alkoxycarbonyl groups, acyl groups, and halogen atoms. Among these polyhydric phenols, dihydric phenols are preferable because a low-viscosity epoxy resin can be obtained even if the vinyl ether modification rate is increased.

  Among the dihydric phenols, bisphenols such as bisphenol A and bisphenol F are superior in terms of performance such as toughness, or because they are excellent in moisture resistance. Therefore, phenols in the phenols / dienes polyadducts A compound in which 1 mol of a diene is added to 2 mol of the compound is preferable.

  Among these, bisphenol A, bisphenol F, bisphenol S, a phenol / dicyclopentadiene adduct, or a phenol / indene adduct is particularly preferable.

  The polyvalent vinyl ethers (a2) are not particularly limited as long as they are compounds containing more than one vinyl ether group in one molecule. For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol Divinyl ether, Tetraethylene glycol divinyl ether, Polyethylene glycol divinyl ether, Propylene glycol divinyl ether, Dipropylene glycol divinyl ether, Tripropylene glycol divinyl ether, Tetrapropylene glycol divinyl ether, Polypropylene glycol divinyl ether, Polytetramethylene glycol Divinyl ethers containing (poly) oxyalkylene groups such as divinyl ether; Roll divinyl ether, triglycerol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanedidiol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10- Divinyl ethers having an alkylene group such as decanediol divinyl ether, neopentyl glycol divinyl ether, and hydroxypivalate neopentyl glycol divinyl ether;

1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecane diol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclopentadecane diol divinyl ether, etc. Divinyl ethers containing a cycloalkane structure; bisphenol A divinyl ether, ethylene oxide modified bisphenol A divinyl ether, propylene oxide modified bisphenol A divinyl ether, bisphenol F divinyl ether, ethylene oxide modified bisphenol F divinyl ether, propylene oxide modified bisphenol F di Divinyl ethers such as vinyl ether; Methylolpropane trivinyl ether, ethylene oxide modified trimethylolpropane trivinyl ether, propylene oxide modified trimethylolpropane trivinyl ether, trivalent vinyl ethers such as pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, pentaerythritol ethoxytetravinyl ether, ditrimethylolpropane tetra Examples include tetravalent vinyl ethers such as vinyl ether; dipentaerythritol hexa (penta) vinyl ether polyvalent vinyl ethers, and the like.

  Among the above polyvalent vinyl ethers, divinyl ethers are preferred because a low-viscosity epoxy resin can be obtained even when the vinyl ether modification rate is increased. Divinyl ethers may be selected appropriately in consideration of the desired properties of the resulting epoxy resin. Among these, divinyl ethers containing a polyoxyalkylene group, divinyl ethers having an alkylene group, and divinyl ethers containing a cycloalkane skeleton are preferable.

  Among these, if low viscosity, excellent flexibility, flexibility, toughness, adhesion, etc. are desired, divinyl ethers containing a polyoxyalkylene skeleton are preferable, and excellent moisture resistance, dielectric properties, heat resistance Is desirable, cycloalkane skeleton-containing divinyl ethers are preferred. The modified polyphenols (A) can be obtained by the above method.

  Examples of these preferred compounds include polyoxyalkylene divinyl ethers having 1 to 6 repeating units (2 to 6 carbon atoms of alkylene group), cyclooctylene divinyl ether, cyclohexylene divinyl ether, tetrahydroxylinylene vinyl ether, tricyclo Examples include decanylene divinyl ether and pentacyclopenta decanylene divinyl ether.

  The modified polyhydric phenols (A) can be obtained by subjecting the polyhydric phenols (a1) and the polyvalent vinyl ethers (a2) to an acetalization reaction described later. Next, the modified polyphenols (A) can be reacted with epichlorohydrin by the method described later to obtain the epoxy resin (B).

  The method for producing the modified polyphenols will be described. As the reaction method, it suffices to follow the reaction conditions of the aromatic hydroxyl group and the vinyl ether group, and is not particularly limited. For example, the polyhydric phenols (a1) and the polyvalent vinyl ethers (a2) The target modified polyhydric phenol can be obtained by charging while stirring and mixing. In this case, an organic solvent and a catalyst can be used as needed. The organic solvent that can be used is not particularly limited, but aromatic organic solvents such as benzene, toluene, xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, Alcohol-based organic solvents such as isopropyl alcohol and normal butanol can be used, and may be appropriately selected in consideration of properties such as the raw materials used and the solubility of the product, reaction conditions, economy, and the like. The amount of the organic solvent is preferably 5 to 500% by weight based on the raw material weight.

  In addition, with respect to the catalyst, the reaction proceeds normally even in a non-catalytic system, but depending on the type of raw material used, the desired properties of the resulting modified polyphenols, the desired reaction rate, etc., the catalyst may be used. May be. The type of the catalyst is not particularly limited as long as it is a catalyst usually used for the reaction of a hydroxyl group and a vinyl ether group. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, toluenesulfonic acid, Methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid and other organic acids, aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide Lewis acids such as boron trifluoride ether complex and boron trifluoride phenol complex can be used, and the addition amount can be in the range of 10 ppm to 1 wt% with respect to the total weight of the raw material. However, in the catalyst addition system, it is necessary to select the type, addition amount, and reaction conditions so as not to cause a vinyl group nucleus addition reaction to the aromatic ring.

  The reaction conditions between the aromatic hydroxyl group and the vinyl ether group are usually room temperature to 200 ° C., preferably 50 to 150 ° C., and may be heated and stirred for about 0.5 to 30 hours. In this case, in order to prevent the self-polymerization of vinyl ethers, the reaction in an oxygen-containing atmosphere is preferable. The progress of the reaction can be traced by measuring the residual amount of the raw material using gas chromatography, liquid chromatography or the like. When an organic solvent is used, it is removed by distillation or the like. When a catalyst is used, it is deactivated with a deactivator if necessary, and then removed by washing with water or filtering. However, in the case of an organic solvent or catalyst (including a deactivated catalyst residue) that does not adversely affect the epoxidation reaction in the next step, there is no need for purification.

  The reaction ratio of polyhydric phenols and polyhydric vinyl ethers in the above reaction is not particularly limited as long as at least one aromatic hydroxyl group remains in one molecule of the reaction product. Depending on the type and combination of polyhydric phenols and polyvalent vinyl ethers, the desired vinyl ether modification rate of the resulting modified polyphenols, physical properties such as molecular weight, hydroxyl equivalent, and acetal conversion rate depending on the reaction conditions, etc. Just decide. For example, if the effects such as flexibility, moisture resistance, and dielectric properties due to vinyl ether modification are to be remarkably enhanced, the amount of polyvalent vinyl ethers may be increased. Specifically, with respect to the aromatic hydroxyl group of the polyhydric phenol, the vinyl ether group of the polyvalent vinyl ether is [aromatic hydroxyl group of the polyhydric phenol] / [vinyl ether group of the polyvalent vinyl ether] = 80 / A ratio of 20 to 50/50 (molar ratio) is preferable. Further, in the case of reaction conditions such that the conversion rate of vinyl ether is low due to the influence of side reaction, the above ratio is [aromatic hydroxyl group of polyhydric phenol] / [vinyl ether group of polyvalent vinyl ether] = 50 / More than 50 (molar ratio), the vinyl ether group excess charge condition may be used. On the other hand, when it is desired to emphasize other physical property balances such as curability and heat resistance, the ratio is [aromatic hydroxyl group of polyhydric phenol] / [vinyl ether group of polyvalent vinyl ether] = 95 / 5-80 / A range of 20 (molar ratio) is preferred.

Of the modified polyphenols obtained as described above, when dihydric phenols are used as the starting polyhydric phenols and divinyl ethers are used as the polyvalent vinyl ethers, the general formula (1)

（式中、ｎは１〜２０の整数を表す。）
で表される化学構造を有する変性ビスフェノール類が主成分として得られる。

(In the formula, n represents an integer of 1 to 20.)
Modified bisphenols having a chemical structure represented by

  Examples of Ar in the general formula (1) include, for example, hydroquinone, resorcin, catechol, dihydroxybenzenes such as these substituent-containing bodies, 1,6-dihydroxynaphthalene, 2 in the polyhydric phenols (a1), , 7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxynaphthalenes such as those containing substituents thereof, bis (4- Hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), 1,1 -Bis (4-hydroxyphenyl) cyclohexane (bi Phenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), bis (4-hydroxyphenyl) sulfone (bisphenol S), bisphenols such as those containing substituents, bis Phenols (naphthols) such as bisnaphthols such as (2-hydroxy-1-naphthyl) methane and bis (2-hydroxy-naphthyl) propane / phenols (naphthols) in a diene adduct And residues obtained by removing a hydroxyl group (—OH) from dihydric phenols to which 1 mol of dienes have been added.

  Among these, as Ar, the structure represented by the residue remove | excluding the hydroxyl group (-OH) from bisphenol A, bisphenol F, bisphenol S, a phenol / dicyclopentadiene adduct, and a phenol / indene adduct is especially preferable.

Specific examples of X in the general formula (1) include a residue obtained by removing a vinyloxy group (—OCH═CH ₂ ) from the divinyl ethers in the polyvalent vinyl ethers (a2).

  Specific examples of the modified polyhydric phenols (A) include, for example, the following structural formula (4), (6) or (8)

で表されるものが挙げられる。（式中、ｎは１〜２０の整数を表す。）

The thing represented by is mentioned. (In the formula, n represents an integer of 1 to 20.)

  Using the modified polyphenols (A) obtained as described above, for example, a method of reacting with epihalohydrins or allyl etherification, the vinyl group is used with peracetic acid or hydrogen peroxide. Thus, the epoxy resin (B) can be obtained by an oxidation method for epoxidation. Among them, a method of reacting with an industrially general epihalohydrin is preferable for reasons such as easy process.

Next, a method of reacting with the epihalohydrins (glycidyl etherification) will be described. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of the modified polyhydric phenol (A) and epihalohydrin such as epichlorohydrin or epibromohydrin, or while adding 20 to 120 The epoxy resin of this invention can be obtained by making it react at 1 degreeC for 1 to 10 hours. The addition amount of epihalohydrin is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of hydroxyl group in the raw material modified polyphenols. When the epihalohydrin is less than 2.5 equivalents, an epoxy group and an unreacted hydroxyl group are likely to react with each other. Therefore, a group formed by an addition reaction between an epoxy group and an unreacted hydroxyl group (—CH ₂ CR (OH) CH ₂ —, A high molecular weight product containing R: a hydrogen atom or an organic carbon group is obtained. On the other hand, when it is more than 2.5 equivalents, the content of the theoretical structure becomes high. The amount of epihalohydrin may be appropriately adjusted according to desired characteristics.

  As the alkali metal hydroxide, an aqueous solution thereof may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously added under reduced pressure or normal pressure. May be distilled off, and the liquid may be further separated to remove water and the epihalohydrin to be continuously returned to the reaction system. Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the modified polyphenols and epihalohydrin and allowed to react at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol resin obtained and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering epihalohydrin or the like is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali such as sodium hydroxide or potassium hydroxide is obtained. An aqueous solution of a metal hydroxide can be added and further reacted to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. The amount of the phase transfer catalyst used is preferably in the range of 0.1 to 3.0% by weight based on the crude epoxy resin.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and an epoxy resin is obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. Of course, it is also possible to use rational means such as preparing modified polyhydric phenols and charging raw materials such as epihalohydrins as they are without continuously removing them from the reactor and continuously converting them to glycidyl ether.

  The epoxy resin thus obtained has the general formula (2)

（式中、Ｘは２価の有機基を示し、両末端の酸素原子（＊）は芳香族環と直接結合している。）で表されるジアセタール構造を分子内に含有するエポキシ樹脂であれば特に限定されるものではない。官能基濃度（エポキシ当量）や官能基数（１分子中のエポキシ基の平均個数）に関しても、特に限定されるものではないが、なかでもエポキシ当量に関しては、１５０〜２０００ｇ／ｅｑ．の範囲が粘度、硬化性、靭性、柔軟性、耐湿性、誘電特性等のバランスに優れることから好ましく、官能基濃度に関しては、１＜官能基数（個）≦２０の範囲が同様な特性バランスに優れることから好ましい。

(In the formula, X represents a divalent organic group, and oxygen atoms (*) at both ends are directly bonded to an aromatic ring.) There is no particular limitation. The functional group concentration (epoxy equivalent) and the number of functional groups (average number of epoxy groups in one molecule) are not particularly limited, but the epoxy equivalent is 150 to 2000 g / eq. Is preferable because it has a good balance of viscosity, curability, toughness, flexibility, moisture resistance, dielectric properties, etc. With regard to the functional group concentration, a range of 1 <number of functional groups (pieces) ≦ 20 has a similar balance of properties. It is preferable because it is excellent.

  Further, when the aforementioned bisphenol type is used as the modified polyhydric phenol as a raw material, the general formula (3)

（式中、Ｇは置換基を有していてもよいグリシジル基を示し、ｎは１〜２０の整数を表す。）で表される２官能型構造を主成分とするエポキシ樹脂が得られる。また、前記一般式（３）中の各基の具体例は、前記一般式（１）中のものと同一である。

(In the formula, G represents an optionally substituted glycidyl group, and n represents an integer of 1 to 20.), an epoxy resin having a bifunctional structure as a main component is obtained. Specific examples of each group in the general formula (3) are the same as those in the general formula (1).

Specific examples of the epoxy resin represented by the general formula (3) include , for example, the following structural formula (5), (7) or (9)

で表されるものが挙げられる。（式中、ｎは１〜２０の整数を表す。）

The thing represented by is mentioned. (In the formula, n represents an integer of 1 to 20.)

The epoxy acrylate resin (C) of the present invention has a structure obtained by reacting the epoxy resin (B) with an ethylenically unsaturated monobasic acid. In the resin structure, the epoxy resin (B) and ethylene The ester bond produced | generated by reaction with a polyunsaturated monobasic acid exists. Specific examples of the ethylenically unsaturated monobasic acid include acrylic acid, methacrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, and methacrylic acid propyl ester. And lower alkyl esters such as acrylic acid and methacrylic acid are preferable from the viewpoint of reactivity and economy.

  The reaction ratio between the epoxy resin (B) and the ethylenically unsaturated monobasic acid is not particularly limited, but the carboxyl group of the ethylenically unsaturated monobasic acid is 0.00 per equivalent of the epoxy group of the epoxy resin. A range of 8 to 1,1 equivalent is preferable, and a range of 0.9 to 1.0 mol is preferable because a resin excellent in photocurability and storage stability is obtained.

  Specific examples of the epoxy acrylate resin (C) include, for example, the following structural formulas (10a), (10b), (12a), (12b), (14a) or (14b)

で表わされるものが挙げられる。（式中、ｎは１〜２０の整数を表す。）

The thing represented by is mentioned. (In the formula, n represents an integer of 1 to 20.)

  Next, the epoxy acrylate resin (D) will be described. The epoxy acrylate resin (D) is an epoxy acrylate resin composed of a compound having an ester bond obtained by reacting a polybasic acid compound with a hydroxyl group in the epoxy acrylate resin (C). is there. The polybasic acid anhydride is not particularly limited. For example, maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydro Phthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) ) Tetrahydrophthalic anhydride, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, phthalic anhydride , Tetrachlorophthalic anhydride, tetrabromophthalic anhydride, anhydrous Lorendic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. are mentioned, but tetrahydrophthalic anhydride and hexahydrophthalic anhydride are particularly preferable because of their excellent electrolytic corrosion properties. preferable.

  The acid value in the epoxy acrylate resin (D) is not particularly limited, but is preferably in the range of 30 to 140 mgKOH / g. In particular, the solubility in an alkaline aqueous solution is good and the developability is excellent. An acid value in the range of 40 to 120 mgKOH / g is particularly preferred from the viewpoint of excellent film characteristics. As described above, the epoxy acrylate resin (D) can be obtained by reacting an epoxy acrylate resin with a polybasic acid anhydride, but the reaction ratio is not particularly limited. The ratio by which the acid anhydride group in a polybasic acid anhydride will be 0.3-1.0 mol with respect to 1 mol of hydroxyl groups in ester resin is mentioned.

  Especially, the acid anhydride group in polybasic acid anhydride is 0 with respect to 1 mol of hydroxyl groups in an epoxy acrylate resin from the point that the solubility with respect to aqueous alkali solution is favorable, and it is excellent in developability, and also the characteristic of a resist coating film. It is preferable to react both at a ratio of 0.5 to 0.8 mol.

  Specific examples of the epoxy acrylate resin (D) include the following structural formula (11), (13) or (15).

で表されるものが挙げられる。（式中、ｎは１〜２０の整数を表す。）

The thing represented by is mentioned. (In the formula, n represents an integer of 1 to 20.)

  The curable resin composition of the present invention will be described. The curable resin composition of the present invention is a composition comprising the above-mentioned epoxy acrylate resin (C) or epoxy acrylate resin (D) and light or a thermal polymerization initiator as essential components. As this photo or thermal polymerization initiator, various initiators generally used for epoxy acrylate resin compositions can be used.

  Examples of the photoinitiator include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- Acetophenones such as 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; methyl anthraquinone, 2-ethylanthraquinone, 2-tert-butyla Anthraquinones such as traquinone, 1-chloroanthraquinone, 2-amylanthraquinone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-diisopropylthioxanthone, etc. Examples include thioxanthones; ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone, and azo compounds, among which acetophenones are preferable.

  These can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate, etc. It can be used in combination with a photoinitiator aid or the like. The amount used is preferably 0.3 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the epoxy acrylate resin (C) or epoxy acrylate resin (D).

  In addition, as the thermal polymerization initiator, a radical polymerization initiator can be used. For example, benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tert-butylperoxide. Peroxides such as oxypiparate, and 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 -Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (methylisobutyrate), α, α-azobis- (isobutyronitrile), 4,4'-azobis- (4-cyanovalein) Examples thereof include azo compounds such as (acid). The usage-amount of a thermal-polymerization initiator is 0.02-60 weight part with respect to 100 weight part of epoxy acrylate resins or epoxy acrylate resin (D), Preferably it is 0.05-2 weight part.

  The alkali-developable photosensitive resin composition is obtained by further blending an epoxy resin (F) with the curable resin composition. Various epoxy resins can be used as the epoxy resin (F), for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy. Resin, Hydroquinone type epoxy resin, Catechol type epoxy resin, Dihydroxynaphthalene type epoxy resin, Biphenyl type epoxy resin, Tetramethylbiphenyl type epoxy resin, etc. Liquid degree epoxy resin, Phenol novolac type epoxy resin, Cresol novolak type epoxy resin, Triphenyl Methane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphtholno Rack type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin Tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin and the like. Moreover, the said other epoxy resin may be used independently and may mix 2 or more types.

  Among them, an epoxy resin having a melting point of 50 ° C. or more is preferable because it can form a photopolymerizable film having no tack after drying. When considering the balance of curability, heat resistance and workability, phenol novolac type epoxy resin and Cresol novolac type epoxy resins and dicyclopentadiene-phenol addition reaction type epoxy resins are preferred. The preferred range of the amount of the epoxy resin (F) used is usually 0.2 to 3.0 equivalents of the epoxy group of the epoxy resin (F) per equivalent of carboxyl group in the epoxy acrylate resin (D). This is the ratio. Among these, a ratio of 1.0 to 1.5 equivalents is preferable from the viewpoint of excellent electrical characteristics when a printed wiring board is used.

  Moreover, in order to accelerate | stimulate reaction with an epoxy acrylate resin (D) and an epoxy resin (F), hardening accelerators of epoxy resins, such as an imidazole, a tertiary amine, and a tertiary amine salt, can also be used.

In addition to the above essential components, a diluent may be used in the curable resin composition. The diluent is dissolved in the epoxy acrylate resin or epoxy acrylate resin (D), applied to have a viscosity suitable for various coating methods such as electrostatic coating method and roll coater method, and then dried and photopolymerized. In the case of forming a conductive film, it is an essential constituent requirement, and usually includes an organic solvent and a photopolymerizable vinyl monomer, but each of them may be used alone or in combination. May be. Examples of the organic solvent used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; Examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as cellosolve, butyl cellosolve and cellosolve acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; and petroleum solvents such as petroleum ether and petroleum naphtha. Among these, it is preferable to use a glycol derivative and a petroleum solvent in combination from the viewpoint of excellent workability.

  Examples of the photopolymerizable vinyl monomer include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) ) Esters of (meth) acrylic acid such as acrylate, benzyl (meth) acrylate and phenoxydiethylene glycol (meth) acrylate; hydroxy such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate Alkyl (meth) acrylates;

  Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Alkylene polyol poly (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate;

  Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethoxylated trimethylolpropane tri (meth) acrylate, polypropoxylated trimethylolpropane tri (meth) acrylate, polyethoxylated Bisphenol A di (meth) acrylate, polypropoxylated bisphenol A di (meth) acrylate, polyethoxylated hydrogenated bisphenol A di (meth) acrylate, polypropoxylated hydrogenated bisphenol A di (meth) acrylate, polyethoxylated dicyclopentaniel Poly (alkylene glycol) poly (meth) acrylates such as di (meth) acrylate and polypropoxylated dicyclopentaniel di (meth) acrylate Over preparative like; poly ester type, such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate (meth) acrylates;

  Isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N -Aminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethylacrylamide, N, N -(Meth) acrylamides such as dimethyl (meth) acrylamide and (meth) acryloylmorpholine; and vinylpyrrolidone. Of these, trifunctional or higher functional acrylates are preferred from the viewpoint of excellent heat resistance of the resist coating film.

  In addition, although the usage-amount of the said diluent is not restrict | limited in particular, 20-300 weight part with respect to 100 weight part of epoxy acrylate resin (C) or an epoxy acrylate resin (D), Especially 30-250 weight The ratio which becomes a part is preferable. Further, the photopolymerizable vinyl monomer promotes photopolymerization, and the water-soluble photopolymerizable vinyl monomer serves to help the solubility in an alkaline aqueous solution, but it is preferable to reduce the photopolymerizable vinyl monomer. After drying, a photopolymerizable film without tack can be formed, the photopolymerizable film and the resist pattern film can be in close contact, the resolution of the resist pattern can be improved, and further, chemical resistance, electrical characteristics, etc. In order to improve, the usage-amount is 50 parts weight or less with respect to 100 weight part of said epoxy acrylate resin or epoxy acrylate resin (D), It is preferable that it is 2-20 weight part especially.

  If necessary, various additives such as fillers such as talc, barium sulfate, silica and clay; thixotropic agents such as aerosil; colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicones and fluorines Leveling agents and antifoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of enhancing the performance of the solder resist ink.

  The curable resin composition of the present invention thus obtained is applied to a printed wiring board by a screen printing method, an electrostatic coating method, a roll coater method, a curtain coater method, and the like, and is obtained by drying. After irradiating the active film with active energy rays such as ultraviolet rays, a resist pattern is formed by removing unexposed portions with a dilute alkaline aqueous solution, and further post-curing with heat to obtain a desired resist film.

  Hereinafter, the present invention will be described by way of examples and comparative examples, but this is only one aspect, and the present invention is not limited to these. All parts and percentages in the examples are based on weight.

Synthesis Example 1 “Synthesis of Modified Polyphenol (A-1)”
A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 184 g (0.91 mol) of triethylene glycol divinyl ether (manufactured by ISP: trade name Rapi-Cure DVE-3), 120 After heating up to 1 ° C. for 1 hour, the mixture was further reacted at 120 ° C. for 6 hours to obtain 412 g of a transparent semi-solid resin. Since the resin obtained peaks of M + = 658 and M + = 1088 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum, the resin having the structure represented by the general formula (4) was obtained. It was confirmed to be a modified polyhydric phenol (A-1). Its hydroxyl equivalent is 353 g / eq. The viscosity was 40 mPa · s (150 ° C., ICI viscometer).

Synthesis Example 2 “Synthesis of Epoxy Resin (B-1)”
In a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 412 g of modified polyphenols ( A-1) obtained in Synthesis Example 1 (hydroxyl equivalent 353 g / eq.), 925 g of epichlorohydrin (10 mol), 185 g of n-butanol was charged and dissolved. Thereafter, while raising the temperature to 65 ° C. while purging with nitrogen gas, the pressure was reduced to an azeotropic pressure, and 12,2 g (1.5 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was continued for 0.5 hours under these conditions. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was conducted while returning the organic layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 20 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 300 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 473 g of a transparent liquid resin. Since the resin obtained peaks of M + = 770 and M + = 1200 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum, the resin having the structure represented by the general formula (5) was obtained. It was confirmed that it was an epoxy resin (B-1). Moreover, the epoxy equivalent of this is 450 g / eq. The viscosity was 15000 mPa · s (25 ° C., Canon Fenceke method).

Synthesis Example 3 “Synthesis of Modified Polyphenols (A-2)”
Modified polyphenols (A-2) were obtained in the same manner as in Synthesis Example 1 except that the amount of triethylene glycol divinyl ether (DVE-3) was changed to 101 g. The hydroxyl group equivalent of the modified polyphenols is 262 g / eq. The viscosity was 60 mPa · s (150 ° C., ICI viscometer).

Synthesis Example 4 “Synthesis of Epoxy Resin (B-2)”
395 g of the target epoxy resin (B-2) was obtained in the same manner as in Synthesis Example 2 except that the raw material modified polyphenols were changed from A-1 to A-2, 329 g. Moreover, the epoxy equivalent of this is 350 g / eq. The viscosity was 90000 mPa · s (25 ° C., E-type viscometer).

Synthesis Example 5 “Synthesis of Modified Polyphenol (A-3)”
A transparent solid resin 372 g was obtained in the same manner as in Synthesis Example 1 except that the raw material DVE-3 was changed to 144 g of 1,4-cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Industries Co., Ltd .: trade name CHDVE). . The resin has a structure represented by the above general formula (6) since peaks of M ⁺ = 652 and M ⁺ = 1076 corresponding to the theoretical structure of n = 1 and n = 2 were obtained in the mass spectrum. It was confirmed that it was the desired modified polyphenols (A-3). Its hydroxyl equivalent is 389 g / eq. The viscosity was 140 mPa · s (150 ° C., ICI viscometer).

Synthesis Example 6 “Synthesis of Epoxy Resin (B-3)”
Transparent solid resins 42 and 2 g were obtained in the same manner as in Synthesis Example 2, except that the raw material modified polyphenols were changed from (A-1) to (A-3) 372 g. The resin has a structure represented by the general formula (7) because a peak of M ⁺ = 764, M ⁺ = 1,188 corresponding to the theoretical structure of n = 1 and n = 2 was obtained in the mass spectrum. It was confirmed that the target epoxy resin (B-3) having Moreover, the epoxy equivalent of this is 490 g / eq. The viscosity was 130 mPa · s (150 ° C., ICI viscometer).

Synthesis Example 7 “Synthesis of Modified Polyphenols (A-4)”
The same as Synthesis Example 1 except that the raw material bisphenol A was changed to 294 g of dicyclopentadiene-modified phenol resin (manufactured by Nippon Oil Chemical Co., Ltd .: trade name Nisishi Special Phenol Resin DPP-6085) and DVE-3 was changed to CHDVE 64 g. As a result, 358 g of a brown solid resin was obtained. The resin has a structure represented by the general formula (8) because a peak of M ⁺ = 836, M ⁺ = 1352 corresponding to a theoretical structure of n = 1 and n = 2 was obtained in the mass spectrum. It was confirmed that it was the desired modified polyphenols (A-4). Its hydroxyl equivalent is 265 g / eq. The viscosity was 710 mPa · s (150 ° C., ICI viscometer).

Synthesis Example 8 “Synthesis of Epoxy Resin (B-4)”
A brown solid resin 429 g was obtained in the same manner as in Synthesis Example 2 except that the raw material modified polyphenols were changed from (A-1) to (A-4) 358 g. The resin has a structure represented by the general formula (9) because peaks of M ⁺ = 948 and M ⁺ = 1464 corresponding to the theoretical structure of n = 1 and n = 2 are obtained in the mass spectrum. It was confirmed that it was the target epoxy resin (B-4). Moreover, the epoxy equivalent of this is 353 g / eq. The viscosity was 190 mPa · s (150 ° C., ICI viscometer).

Example 1
450 parts of the epoxy resin (B-1) obtained from Synthesis Example 2 and 72 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1, 1) were reacted to obtain 52, 2 parts of a resin. . The resin has a structure represented by the general formula (10) because a peak of M ⁺ = 842 and M ⁺ = 1272 corresponding to the theoretical structure of n = 1 and n = 2 was obtained in the mass spectrum. It was confirmed that it was the target epoxy acrylate resin (C-1). Further, 52,2 parts of epoxy acrylate resin (C-1) and 137 parts of tetrahydrophthalic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.9) were reacted in 282 parts of butyl carbitol acetate. Thus, a resin solution (D′-1) containing 70% of a resin having an acid value of 76 mgKOH / g was obtained. In this resin solution (D′-1), a peak of M ⁺ = 976, M ⁺ = 1406 corresponding to the theoretical structure of n = 1 and n = 2 was obtained in the mass spectrum. It was confirmed that the target epoxy acrylate resin (D-1) having the structure represented by 1a) was contained.

A photopolymerization initiator, an organic solvent and a filler were blended together with the resin solution (D′-1) as follows, and kneaded using a three-roll mill to prepare a main agent. Next, an epoxy resin, an organic solvent, and an emphasis agent were blended according to the following blending and kneaded using three rolls to prepare a curing agent.
(Combination)
Main agent (total 100 parts); [Resin solution (D′-1) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, Butyl cellosolve 15 parts, Barium sulfate 30 parts Main agent total]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLONN-680” (manufactured by Dainippon Ink and Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts, barium sulfate 10 parts]

  Next, after mixing the main agent and the curing agent, the mixture is made into a thickness of 15 to 25 μm on a flexible printed wiring board (Kapton 25 μm / copper foil 35 μm, line width 500 μm, line spacing 500 μm) on which a circuit is formed in advance. After being applied to the entire surface by screen printing and dried at 80 ° C. for 20 minutes, the resist pattern film is brought into close contact with the coated surface and exposed for 60 seconds using a metal halide lamp exposure apparatus manufactured by Oak Manufacturing Co., Ltd. Development was performed for 60 seconds using a 1% sodium carbonate aqueous solution at a temperature of 30 ° C., and then heat treatment was performed at 150 ° C. for 30 minutes using a hot air dryer to obtain a flexible printed wiring board on which a resist pattern was formed. Next, Table 1 shows the results measured according to the following evaluation test method.

Example 2
Epoxy acrylate resin (C) obtained by reacting 350 parts of epoxy resin (B-2) obtained from Synthesis Example 4 and 72 parts of acrylic acid (number of epoxy groups: total number of carboxyl groups = 1, 1) -2) Reaction of 42,2 parts with 12,2 parts of tetrahydrophthalic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.8) in 233 parts of butyl carbitol acetate A resin solution (D′-2) containing 70% of an epoxy acrylate (D-2) having a value of 82 mgKOH / g was obtained.

Subsequently, a solder printed ink composition of the present invention was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (total 100 parts); [resin solution (D′-2) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts total main agent]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLONN-680” (Dainippon Ink & Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts barium sulfate 10 parts]

Example 3
490 parts of the epoxy resin (B-3) obtained from Synthesis Example 6 and 72 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1, 1) were reacted to obtain 562 parts of a resin. The resin has a structure represented by the above general formula (12a) because peaks of M ⁺ = 836 and M ⁺ = 1260 corresponding to the theoretical structure of n = 1 and n = 2 were obtained in the mass spectrum. It was confirmed that it was the target epoxy acrylate resin (C-3). Further, 562 parts of epoxy acrylate resin (C-3) and 137 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.9) were reacted in 300 parts of butyl carbitol acetate. A resin solution (D′-3) containing 70% of a resin having an acid value of 72 mgKOH / g was obtained. In this resin solution (D′-3), peaks of M ⁺ = 970 and M ⁺ = 1394 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum were obtained, so that the above general formula (13a) It was confirmed that the target epoxy acrylate resin (D-3) having a structure represented by the formula: Next, a solder resist ink composition was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (100 parts in total); [resin solution (D′-3) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts]
Curing agent (100 parts in total); [cresol novolak type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink and Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts, barium sulfate 10 parts]

Example 4
The resin 425 parts was obtained by reacting 353 parts of the epoxy resin (B-4) obtained from Synthesis Example 8 and 72 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1, 1). The resin has a structure represented by the above general formula (14a) because peaks of M ⁺ = 1020 and M ⁺ = 1536 corresponding to the theoretical structure of n = 1 and n = 2 were obtained in the mass spectrum. It was confirmed that it was the target epoxy acrylate resin (C-4). Further, 425 parts of epoxy acrylate resin (C-4) and 12,2 parts of tetrahydrophthalic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.8) were reacted in 234 parts of butyl carbitol acetate. Thus, a resin solution (D′-4) containing 70% of a resin having an acid value of 82 mgKOH / g was obtained. In this resin solution (D′-4), peaks of M ⁺ = 1,154 and M ⁺ = 1670 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum were obtained. It was confirmed that the target epoxy acrylate resin (D-4) having the structure represented by 15a) was contained.
Subsequently, a solder printed ink composition of the present invention was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (total 100 parts); [resin solution (D′-4) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink & Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts, barium sulfate 10 parts]

Comparative Example 1
Epoxy equivalent was 188 g / eq. BPA liquid epoxy resin EPICLON 850 (manufactured by Dainippon Ink and Chemicals, Inc.) 188 parts and 72 parts of acrylic acid (number of epoxy groups: total number of carboxyl groups = 1, 1) obtained epoxy 260 parts of acrylate resin and 91 parts of tetrahydrophthalic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.6) were reacted in 150 parts of butyl carbitol acetate to give an acid value of 96 mgKOH / g A resin solution (D′-5) containing 70% of the epoxy acrylate was obtained.

Next, a comparative solder resist ink composition was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (total 100 parts); [resin solution (D′-5) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink & Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts, barium sulfate 10 parts curing agent total 30 parts]

Comparative Example 2
Epoxy equivalent is 475 g / eq. BPA type solid epoxy resin “EPICLON1050” (Dainippon Ink Chemical Co., Ltd.) 475 parts and acrylic acid 72 parts (number of epoxy groups: total number of carboxyl groups = 1, 1) 547 parts of epoxy acrylate resin and 137 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.9) were reacted in 293 parts of butyl carbitol acetate to give an acid value of 74 mgKOH. A resin solution (D′-6) containing 70% of / g epoxy acrylate was obtained.

Next, a comparative solder resist ink composition was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (total 100 parts); [resin solution (D'-6) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink & Chemicals, Inc.) 15 parts, butyl cellosolve 5 parts, barium sulfate 10 parts]

Comparative Example 3
Epoxy equivalent is 215 g / eq. 215 parts of cresol novolac type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink & Chemicals, Inc.) and 72 parts of acrylic acid (number of epoxy groups: number of total carboxyl groups = 1, 1) 287 parts of the obtained epoxy acrylate resin and 106 parts of tetrahydrophthalic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1: 0.7) were reacted in 168 parts of butyl carbitol acetate to give an acid. A resin solution (D′-7) containing 70% of an epoxy acrylate having a value of 100 mgKOH / g was obtained.

Next, a comparative solder resist ink composition was prepared in the same manner as in Example 1 except that the following composition was used, and then a flexible printed wiring board on which a resist pattern was formed was obtained in the same manner. Next, Table 1 shows the results measured according to the following evaluation test method.
(Combination)
Main agent (total 100 parts); [resin solution (D′-7) 50 parts, 2,2-dimethoxy-2-phenylacetophenone 5 parts, butyl cellosolve 15 parts, barium sulfate 30 parts]
Curing agent (curing agent total 30 parts); [cresol novolac type epoxy resin “EPICLONN-680” (manufactured by Dainippon Ink & Chemicals, Inc.) 15 parts butyl cellosolve 5 parts barium sulfate 10 parts]

[Evaluation test method]
Adhesiveness: Using a flexible printed wiring board on which a resist pattern was formed, a cross cut was made in a grid pattern according to a test method of JIS D-2020, and then a peel test was performed with a cellophane tape.
○: No peeling at all 100 measurement points.
(Triangle | delta): The thing from which peeling was recognized by the point of 1-50 among 100 measurement points.
X: The thing by which peeling was recognized by the point of 51-100 in 100 measurement points.

Flexibility: 180 ° outer fold inward fold test (MIT test) Judgment was made by the number of folds until a crack was generated by R = 4 mmφ.
Solder heat resistance: A flexible printed wiring board on which a resist pattern is formed is floated in a 260 ° C. solder bath for 10 seconds in accordance with a test method of JIS C-6481. This was defined as one cycle, and after floating, the number of cycles until an abnormality such as swelling or peeling occurred in the coating film was measured.

  Insulation resistance: A flexible printed wiring board on which a resist pattern is formed is applied to 24 V in an atmosphere of 60 ° C. and 90% RH, and the insulation resistance value after 400 hours is used with SM-10E (500 V applied) manufactured by Toa Denpa. Measured.

It can be used not only as a flexible solder resist ink but also as a permanent protective film such as an overcoat, an undercoat, an insulation coat of a printed wiring board, an interlayer insulation material of a build-up board, and the like.

Claims (10)

An epoxy resin (B) obtained by converting a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2) into a glycidyl ether, An epoxy acrylate resin obtained by reacting a basic acid. The epoxy acrylate resin according to claim 1, wherein the polyvalent vinyl ethers (a2) are divinyl ethers. The divinyl ether is a polyoxyalkylene divinyl ether having 1 to 6 repeating units (2 to 6 carbon atoms of an alkylene group), cyclooctylene divinyl ether, cyclohexylene divinyl ether, tetrahydroxylylene divinyl ether, tricyclodecanylene diene The epoxy acrylate resin according to claim 2, which is at least one divinyl ether selected from the group consisting of vinyl ether and pentacyclopentadecanylene divinyl ether. 2. The epoxy acrylate resin according to claim 1, wherein the polyhydric phenol (a1) is a compound obtained by adding 1 mol of a diene to 2 mol of a phenol in a bisphenol or a phenol / diene polyaddition product. The epoxy acrylate resin according to claim 4, wherein the dihydric phenol is bisphenol A, bisphenol F, bisphenol S, a phenol / dicyclopentadiene adduct, or a phenol / indene adduct. An epoxy acrylate resin obtained by further reacting a polybasic acid compound with the epoxy acrylate resin according to any one of claims 1 to 5. A curable resin composition comprising the epoxy acrylate resin according to claim 1 and light or a thermal polymerization initiator (E). An alkali development type photosensitive resin composition comprising the epoxy acrylate resin according to claim 6, a photopolymerization initiator, and an epoxy resin (F). A cured product obtained by curing the curable resin composition according to claim 7. A cured product obtained by curing the curable resin composition according to claim 8.