KR100865614B1 - Acid Modified Epoxy metaAcrylate Compound, Method of Manufacturing the same, Photosensitive Thermosetting Resin Composite containing the Compound, and Hardened Material of the Composite - Google Patents

Abstract

Liquid solder resist used in the manufacture of printed wiring boards, especially IC packages such as BGAs (ball grid arrays) and CSPs (chip scale packages) using printed resistive printed wiring boards and encapsulating resins In the field of electronic materials of inks and dry film resistors, in the cold heat cycle test, which is one of the mounting and long-term reliability tests, cracks do not occur in the cured film, and the dryness, alkali developability, development life, and PCT are not cracked. The acid-modified epoxy (meth) acrylate compound and the acid-modified epoxy (meth) acrylate compound suitable for forming a film excellent in resistance, solder heat resistance, adhesion to substrates, hardness, electroless gold plating resistance and electroless tin plating resistance, It provides the photosensitive thermosetting resin composition containing.

To an unsaturated group-containing dicarboxylic acid compound obtained by reacting a tribasic acid, a tetrabasic acid, or an acid anhydride (ai) of a tribasic acid and a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii), 2 in 1 molecule. Epoxy compound (a) containing unsaturated group which has two epoxy groups in 1 molecule represented by following General formula (1) obtained by making epoxy compound (a-iii) which has two epoxy groups react, and unsaturated group containing monocarboxylic acid (b) Acid-modified epoxy (meth) acrylate compound (I) obtained by reacting a polybasic acid anhydride (c) with a reaction product obtained by reacting a compound), an epoxy compound (II) having two or more epoxy groups in one molecule, and a photopolymerization The said subject can be achieved by the alkali developable photosensitive thermosetting resin composition which contains an initiator (III) and a diluent (IV) as an essential component.

General formula (1)

(Formula 1)

(Wherein M is a hydrogen atom or

(Formula 2)

Wherein at least one of M

(Formula 3)

X is the same or different bases selected from divalent aromatic, alkyl or cyclohexyl groups, and Y is the same or different aromatics selected from trivalent or tetravalent aromatic groups A is a residue of an unsaturated group-containing monoalcohol, and n is an integer of 1 to 100.)

Printed wiring board, solder resist, acrylate, thermosetting resin

Description

Acid Modified Epoxy (Meta) Acrylate Compound, Method for Manufacturing the Same, Photosensitive Thermosetting Resin Composition Containing the Compound, and Cured Product Thereof (Acid Modified Epoxy (meta) Acrylate Compound, Method of Manufacturing the same, Photosensitive Thermosetting Resin Composite containing the Compound , and Hardened Material of the Composite}

The present invention is in the field of commercial and industrial printed wiring boards and IC packages such as BGAs (ball grid arrays) and CSPs (chip scale packages) using printed wiring boards and encapsulating resins subjected to solder resist. Acid-denatured epoxy (meth) acrylate compounds useful for liquid solder resist ink and dry film type solder resist capable of forming an image in a rare alkali developer used for the production of printed wiring boards, and methods for producing the same It relates to the photosensitive thermosetting resin composition containing a compound, and its hardened | cured material.

(Patent Document 1) Japanese Patent Application Laid-Open No. 61-243869

(Patent Document 2) Japanese Patent Application Laid-Open No. 3-253093

(Patent Document 3) Japanese Patent Application Laid-Open No. 11-288091

(Patent Document 4) Japanese Patent Application Laid-Open No. 11-315107

(Patent Document 5) Japanese Patent Application Laid-Open No. 11-242331

(Patent Document 6) Japanese Patent Application Laid-Open No. 2001-278947

(Patent Document 7) Japanese Unexamined Patent Application Publication No. 2000-321765

(Patent Document 8) Japanese Patent Application Laid-Open No. 2002-90994

(Patent Document 9) Japanese Unexamined Patent Application Publication No. 4-170480

(Patent Document 10) Japanese Unexamined Patent Publication No. 4-170481

The manufacture of current printed wiring boards has the purpose of protecting lead parts from sticking to unneeded parts when soldering and mounting electronic components to printed wiring boards after wiring (circuit) pattern formation. In order to protect a circuit from the back and the like, coating of a protective layer called a solder mask is performed.

The soldering resist used for the said printed wiring board apply | coats the liquid solder resist ink of ultraviolet curing type or thermosetting type, or photo developing type which uses ultraviolet curing and thermosetting together on a printed wiring board by printing methods, such as screen printing. Although a type can be obtained by attaching a dry film resistor that does not contain an organic solvent having a polyester film or a polyethylene film as a support to a printed wiring board and peeling the support, a high precision and high-density viewpoint and environment are known. Photo-developmental type which uses a alkali solution as a developing solution is mainstream from consideration to the main body, The negative film which has an image pattern is put on a film, and it develops with a alkali solution, after photocuring (temporal hardening) by ultraviolet irradiation. Is formed, and the film is obtained by thermosetting (main curing). .

Phenol novolak-type acid-modified epoxy acrylate compounds and epoxy compounds, which are most widely used as conventional alkali developing solder resists conventionally used in printed circuit boards for IC packages, include, for example, patent documents 1 and 2), the cured coating is a reflow step in package mounting, a cold heat cycle test (cycle test at -65 ° C and 125 ° C), which is one of long-term reliability tests, and package manufacture. The problem that a crack generate | occur | produces in the hardened film is caused in the process of metal mold shaping | molding by the sealing resin in etc., and improvement is calculated | required. Such a problem is not limited only to the above-described mounting technique, and is not preferable even in the solder resist of a general printed wiring board.

Various attempts have been made on such a problem so far. For example, there are a reaction product in which a phenol compound and / or a naphthol compound and an unsaturated group-containing monocarboxylic acid are reacted with a novolak-type epoxy compound, and a polybasic acid anhydride is reacted, and a register ink containing an epoxy compound as an essential component ( See, for example, Patent Documents 3 and 4). Although this resist ink gives flexibility to the cured film formed and solves crack resistance, it does not have sufficient alkali developability and causes the problem that image formation of a clear resist pattern is difficult. In addition, a reaction product in which an epoxy compound selected from a bisphenol F-type epoxy compound or a rubber-modified epoxy compound is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is reacted with a resist ink containing an epoxy compound as an essential component (e.g., For example, refer to Patent Document 5), a bisphenol-type polyfunctional epoxy compound having a specific structure and an unsaturated group-containing monocarboxylic acid are reacted, and further, a reaction product obtained by reacting a polybasic acid anhydride and an epoxy compound as essential components. There is a register ink to make a reference (for example, refer patent document 6). Such resist inks are provided with flexibility to the cured film formed and resolved crack resistance. However, all of these resist inks have low sensitivity in ultraviolet light (light), so that the resolution of the formed image is low, and high density packaging is required for the next generation. The problem of not being able to cope sufficiently is concerned.

Furthermore, an epoxy compound selected from a novolak-type epoxy compound, a glycol-based epoxy compound, or a mixture thereof, a reaction product containing an unsaturated group-containing monocarboxylic acid and a saturated monocarboxylic acid, and a polybasic acid anhydride are reacted with an epoxy compound. A resist ink containing an essential component is reacted with an epoxy compound, a compound having one functional group selected from an alcoholic hydroxyl group, a carboxyl group and an amino group, and an unsaturated group-containing monocarboxylic acid in one molecule, There is a reaction product on which polybasic acid anhydride is reacted (see Patent Document 8, for example). In addition, the reaction product of an acid anhydride of tribasic acid or more with 2-hydroxyethyl (meth) acrylate alone or a mixture of it and (meth) acrylic acid may be epoxy compound or epoxy (meth) acryl such that the carboxyl group remains unreacted. Although there are reaction products reacted with the rate (see, for example, Patent Documents 9 and 10), all of the cured films formed are given flexibility and crack resistance is solved, but similar to crack resistance, PCT is one of long-term reliability tests. (Pressure Cooker Test) Problems arise that the resistance is not sufficient, the development life during the solvent drying step of the coating is remarkably short, and it is difficult to form a wiring pattern in a printed wiring board. Furthermore, in the said patent document 7, when the amount of saturated monocarboxylic acid is mix | blended in order to adjust the degree of flexibility, the problem that the touch-drying property after the solvent drying process of a coating falls remarkably arises, and also in the said patent document 9 In order to maintain the development life, there arises a problem of requiring an expensive microencapsulated thermosetting catalyst.

Thus, when flexibility is provided to the cured film formed in order to solve crack resistance, either one of alkali developability or PCT resistance falls generally, and the development life and solvent in a solvent drying process The touch-drying property, alkali developability, development life, PCT resistance, solder of film which is a basic performance as a solder resist ink used for manufacture of a printed wiring board of a semiconductor package, such as the touch-drying property after a drying process falls. It is extremely difficult to completely solve the crack problem of the cured film which arises at the balance of heat resistance, adhesiveness with a base material, the hardness of a film, etc., and at the time of mounting and the cold heat cycle test of a long-term reliability test, and is fully satisfied until now. There is nothing to do.

Furthermore, in recent years, in response to environmental movements in printed wiring boards, with the lead-freeization, an electroless tin plating resistance is required for the hardened film of the solder resist, but an epoxy sufficiently satisfying the electroless tin plating resistance It is a reality that a (meth) acrylate compound does not exist.

Therefore, the object of the present invention is to use for the manufacture of printed wiring boards, in particular for the production of IC packages such as BGAs (ball grid arrays) and CSPs (chip scale packages) using a printed wiring board subjected to solder resist and a sealing resin. In the field of liquid solder resist inks and dry film resistors, the dry film, alkali developability, development life without cracking the cured film formed in the cold heat cycle test, which is one of the mounting and long-term reliability tests. , An acid-modified epoxy (meth) acrylate compound suitable for forming a film having excellent PCT resistance, solder heat resistance, adhesion to a substrate, hardness, and excellent gold plating resistance and tin plating resistance, a method for producing the same, and a photosensitive thermosetting containing the compound It is to provide a resin composition and the like.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered the acid-modified epoxy (meth) acrylate compound which has a novel structure which is very suitable for achieving the said objective, and its manufacturing method, and said acid-modified The cured film in which the photosensitive thermosetting resin composition which mix | blended an epoxy compound, a photoinitiator, and a diluent as an essential component in an epoxy (meth) acrylate compound shows the characteristic with a good balance with respect to the characteristic over various directions as mentioned above. The present invention was found to provide a cured product which is remarkably excellent in crack resistance and excellent in electroless gold plating resistance and electroless tin plating resistance.

Acid-modified epoxy (meth) acrylate compounds found by the inventors of the present invention to achieve the above object is represented by the following formula (1).

delete

delete

(Formula 1)

(Wherein M is a hydrogen atom or

(Formula 2)

Wherein at least one of M

(Formula 3)

X is the same or different groups selected from divalent aromatic, alkyl and cyclohexyl groups, and Y is the same or different aromatics selected from trivalent or tetravalent aromatic groups A is a residue of an unsaturated group-containing monoalcohol, Q is a residue of an unsaturated group-containing monocarboxylic acid, G represents a residue of a polybasic acid containing at least one hydrogen atom or at least one carboxyl group, and at least one of G is Is a residue of a polybasic acid, n is an integer from 1 to 100.)

The acid-modified epoxy (meth) acrylate compound of the general formula (1) reacts an unsaturated group-containing epoxy compound (a) having two epoxy groups with an unsaturated group-containing monocarboxylic acid (b) in one molecule represented by the following formula (4) It is manufactured by making a polybasic acid anhydride (c) react with the obtained reaction product.

delete

delete

delete

delete

(Formula 4)

(Wherein M is a hydrogen atom or

(Formula 5)

Wherein at least one of M

(Formula 6)

X is the same or different groups selected from divalent aromatic, alkyl and cyclohexyl groups, and Y is the same or different aromatic groups selected from trivalent or tetravalent aromatic groups ), A is a residue of an unsaturated group-containing monoalcohol, and n is an integer of 1 to 100.
Moreover, the unsaturated group containing epoxy compound (a) which has two epoxy groups in 1 molecule is tribasic acid, tetrabasic acid, or acid anhydride (ai) of tribasic acid and tetrabasic acid, and unsaturated group containing monoalcohol (a- You may manufacture by making the epoxy group (a-iii) which has two epoxy groups in 1 molecule react with the unsaturated group containing dicarboxylic acid compound obtained by making ii) react.
The photosensitive thermosetting resin composition is an epoxy having two or more epoxy groups in one molecule per carboxyl equivalent of the acid-modified epoxy (meth) acrylate compound (I) and the acid-modified epoxy (meth) acrylate compound (I) 0.1-30 weight per 100 weight part of epoxy compound (II) and acid-modified epoxy (meth) acrylate compound (I) which have two or more epoxy groups in 1 molecule of the epoxy group of compound (II) in the quantity corresponding to 0.1-1.5 equivalents It is produced by mixing 1 to 300 parts by weight of diluent (IV) per 100 parts by weight of the negative photopolymerization initiator (III) and the acid-modified epoxy (meth) acrylate compound (I).
The configuration of the present invention will become more apparent in the best mode for carrying out the following invention.

(The best mode for carrying out the invention)

In this specification, (meth) acrylic acid is acrylic acid, methacrylic acid, or such a mixture is epoxy (meth) acrylate, an epoxy acrylate, an epoxy methacrylate, or such a mixture is a (meth) acrylic acid ester, Acrylic esters, methacrylic esters. Or such mixtures.

The present invention has two epoxy groups in one molecule of an unsaturated group-containing dicarboxylic acid compound obtained by reacting an acid anhydride (ai) of a tribasic acid or a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii). Obtained by making the unsaturated group containing epoxy compound (a) and unsaturated group containing monocarboxylic acid (b) which have two epoxy groups react in 1 molecule represented by following General formula (1) obtained by making an epoxy compound (a-iii) react The acid-modified epoxy (meth) acrylate compound, the acid-modified epoxy (meth) acrylate compound (I), and two or more epoxy groups in 1 molecule are formed by reacting the reaction product with a polybasic acid anhydride (c). The photosensitive thermosetting resin composition which contains an epoxy compound (II), a photoinitiator (III), and a diluent (IV) as an essential component, and the said photosensitive thermosetting property It is providing the hardened | cured material which has the outstanding film characteristic obtained by hardening | curing a resin composition.

General formula (1)

(Formula 7)

(Wherein M is a hydrogen atom or

(Formula 8)

Wherein at least one of M

Formula 9

X is the same or different group selected from a divalent aromatic group, an alkyl group, a cyclohexyl group, Y is the same or different aromatic group selected from a trivalent or tetravalent aromatic group, and A is unsaturated It is a residue of group containing monoalcohol, n is an integer of 1-100.)

In addition to the characteristics of the hardened | cured material obtained by hardening | curing the photosensitive thermosetting resin composition containing the acid-modified epoxy (meth) acrylate compound in this invention, having the outstanding crack resistance in PCT tolerance of this subject or a cold heat cycle test, In order to combine electroless gold plating resistance, electroless tin plating resistance, or electroless gold plating resistance and electroless tin plating resistance, it is important to select the structures of X and Y in addition to the basic structure of the general formula (1).

X in the said General formula (1) represents the same or different group chosen from the bivalent aromatic group, alkyl group, and cyclohexyl group of following (d)-(m), For example, (d) , (e), (l), and (m), R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Or a halogen atom, a, b, c, d, i, j, k, l are _{1 when} R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ are alkyl groups It is -4 and it is 1 or 2 when it is a halogen atom. In (f), (g) and (j), R ₅ , R ₆ , R ₇ , and R ₈ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and e, f, g are 1 to 4, and h is 1 Is ~ 4. In addition, R <_9> in (k) is a C1-C12 alkyl group, R <_14> , R <_15> in (m) is the same / or another C1-C3 alkyl group. Moreover, Z <_1> , Z <_2> , Z <_3> in (e), (l), (m) is alkylene, cycloalkylene, halogen, cyclokill or aryl substituted alkylene, sulfur atom, sulfur monoxide, or Sulfur dioxide.

Formula 10

Formula 11

(Formula 12)

(Formula 13)

(Formula 14)

(Formula 15)

(Formula 16)

(Formula 17)

Formula 18

(Formula 19)

Y in the said General formula (1) is the same or different aromatic groups chosen from the trivalent or tetravalent aromatic groups of (n)-(u) below, A represents the residue of an unsaturated-group containing monoalcohol For example, Z <_4> in (r) below is an oxygen atom or a carbonyl group, a C1-C4 alkyl group, and sulfur dioxide, and Z <_5> in (s) below is a C1-C4 alkyl group. .

(Formula 20)

Formula 21

(Formula 22)

(Formula 23)

(Formula 24)

(Formula 25)

Formula 26

Formula 27

First, the acid-modified epoxy (meth) acrylate compound (I) which is 1st invention of this invention is demonstrated. Acid-modified epoxy (meth) acrylate compound (I) in this invention is a compound which consists of a structure which has a photosensitive double bond and a carboxyl group which can be radically polymerized in a molecule | numerator, and the photocuring process by ultraviolet (light) irradiation Radical polymerization in the presence of photopolymerization initiator (III) coexisting to form a cured product (temporary curing). At this time, the part to which ultraviolet-ray (light) is not irradiated is removed in the image development process which used the aqueous alkali solution in the presence of the carboxyl group in a molecule | numerator, and an image is drawn. On the other hand, the carboxyl group in the hardened | cured material (temporary hardening) which is not removed by an alkali image development process reacts with the epoxy compound (II) which coexists in a thermosetting process (main hardening), and forms a strong bond.

Said acid-modified epoxy (meth) acrylate compound (I) is the unsaturated compound containing epoxy group (a) and unsaturated group containing mono which have two epoxy groups in 1 molecule represented by the said General formula (1), for example. The polybasic acid anhydride (c) in the alcoholic hydroxyl group in the molecule | numerator of the reaction product obtained by making carboxylic acid (b) react with 60-150 degreeC in presence of a well-known catalyst and a polymerization inhibitor, and in inert gas stream or presence of air. ) Can be produced by reacting at 30 ~ 150 ℃.

The acid-modified epoxy (meth) acrylate compound of the present invention is as follows.

That is, the acid-modified epoxy (meth) acrylate compound of the present invention,

The following general formula:

Formula 28

(Wherein M is a hydrogen atom or

(Formula 29)

Wherein at least one of M

(Formula 30)

X is the same or different group selected from divalent aromatic group, alkyl group, cyclohexyl group, Y is the same or different aromatic group selected from trivalent or tetravalent aromatic group, and A is unsaturated Is a residue of a group-containing monoalcohol, Q is a residue of an unsaturated group-containing monocarboxylic acid, G represents a residue of a polybasic acid containing at least one hydrogen atom or at least one carboxyl group, at least one of G is a residue of a polybasic acid and n is 1 Is an integer of ~ 100).

First, the unsaturated compound containing epoxy compound (a) which has two epoxy groups in 1 molecule represented by the said General formula (1) is demonstrated.

The unsaturated group-containing epoxy compound (a) having two epoxy groups in the above one molecule is a tribasic acid, a tetrabasic acid, or an acid anhydride (ai) of a tribasic acid and a tetrabasic acid and an unsaturated group-containing monoalcohol (a- Unsaturated trivalent or tetravalent aromatic groups shown in (n) to (u) obtained by reacting ii) with a known catalyst and a polymerization inhibitor and reacting at 30 to 150 ° C in an inert air stream or in the presence of air. Epoxy compound which has the same or different group selected from group containing dicarboxylic acid compound, the divalent aromatic group, alkyl group, and cyclohexyl group shown to said (d)-(m), and has two epoxy groups in 1 molecule It can obtain by making (a-iii) react at 60 degreeC-150 degreeC. The reaction of the tribasic acid, tetrabasic acid or the acid anhydride (ai) of the tribasic acid and the tetrabasic acid with the unsaturated group-containing monoalcohol (a-ii) is monounsaturated group-containing mono, which will be described later for the purpose of lowering the viscosity during the reaction. A part or whole amount of carboxylic acid (b) may be added, the diluent (IV) mentioned later may be added, or a part or whole quantity and a diluent (IV) of monocarboxylic acid (b) containing an unsaturated group may be added.

In addition, the reaction of an acid anhydride (ai) of a tribasic acid, a tetrabasic acid or a tribasic acid and a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii), and 2 in 1 molecule of the general formula (1) Reaction of the reaction product and polybasic acid anhydride (c) which made the unsaturated compound containing epoxy group (a) and unsaturated group containing monocarboxylic acid (b) which have two epoxy groups react with is the absorption wavelength peculiar to an acid anhydride (1780 cm) from IR measurement. ^-1 ) was confirmed by the presence or absence. In addition, an unsaturated group-containing dicarboxylic acid compound which is a reaction product of a tribasic acid, a tetrabasic acid, or an acid anhydride (ai) of a tribasic acid and a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii) and 2 in 1 molecule Reaction of the epoxy compound (a-iii) and unsaturated group containing monocarboxylic acid (b) which have two epoxy groups was confirmed by the measurement of the acid value (unit is mgKOH / g) described in JISK6901.

As said tribasic acid, tetrabasic acid, or the acid anhydride (ai) of a tribasic acid and a tetrabasic acid, For example, tribasic acid anhydrides, such as trimellitic anhydride, a pyromellitic anhydride, a biphenyl tetracarboxylic acid. 4, such as dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, ethylene glycol-bis (trimellitic dianhydride) ester Basic acid anhydride is mentioned. These tribasic acid anhydrides and tetrabasic acid anhydrides can be used individually or in combination of 2 or more types.

Said unsaturated group containing monoalcohol (a-ii) is monoalcohol which shows radically polymerizable, For example, 2-hydroxy ethyl (meth) acrylate, 3-hydroxy propyl (meth) acrylate, 4 -Hydroxy butyl (meth) acrylate, 1,4-cyclohexyl dimethanol mono (meth) acrylate, trimethylpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, (meth) acrylic acid And caprolactone adducts. These can be used individually or in combination of 2 or more types.

The reaction of tribasic acid, tetrabasic acid, or acid anhydride (ai) of tribasic acid and tetrabasic acid with unsaturated alcohol-containing monoalcohol (a-ii) is prepared by a known method, but the combination is tribasic acid, To 1 equivalent of tetrabasic acid or acid anhydride (ai) of tribasic acid and tetrabasic acid, the range of 1 to 5 equivalents, preferably 1 to 2 equivalents of unsaturated group-containing monoalcohol (a-ii) In the presence or absence of a catalyst, presence of a polymerization inhibitor, and further in the presence or absence of a diluent (IV) described below, in the presence of an inert gas stream or air, and a reaction temperature of 30 to 150 ° C. Preferably, it is 60-100 degreeC, More preferably, it is 80-95 degreeC, and reaction time makes it react for 0.5 to 30 hours. In the reaction, when the reaction temperature is less than 30 ° C, unreacted acid anhydride remains, which may cause gelation in subsequent reactions. On the other hand, at a high temperature where the reaction temperature exceeds 150 ° C, the Michael addition reaction may occur as a side reaction and the molar balance in the subsequent reaction may collapse, which may cause gelation. However, if gelation etc. can be suppressed, reaction temperature is not specifically limited.

Although the said epoxy compound (a-iii) which has two epoxy groups in 1 molecule is not specifically limited, A well-known method combining phenols which have two phenolic hydroxyl groups in 1 molecule individually or in combination of 2 or more types It can be prepared by epoxidizing with epichlorohydrin.

Moreover, a commercially available epoxy compound can also be used for the epoxy compound (a-iii) which has two epoxy groups in the said one molecule. As a commercially available epoxy compound, for example, the brand name "Epicoat 828" which is a product made by Japan epoxy resin company, "Epicoat 834", "Epicoat 1001", "Epicoat 1004", the brand name "Epiclon" which is a product made by Japan Ink Chemical Industries, Ltd. 840 "," Epicron 850 "," Epicron 1050 "," Epicron 2055 ", the brand name" Efototo 128 "which is manufactured by Toto Chemical Co., Ltd., and the product name" D. E. R. 317, "D. E. R. 331, `` D. E. R.661, `` D. ER664, brand name `` AER250 '', `` AER260 '', `` AER2600 '', product name `` Sumiepoxy ESA-011 '', `` Sumiepoxy ESA-014 '', `` Sumiepoxy ELA-128 '' which are products of Asahi Kasei Chemicals Co., Ltd. Bisphenol A type epoxy compounds, the brand name "Epicron 830S" which are the products of Japan Ink Chemicals, etc., the brand name "Epicoat 807" which is a product of Japan epoxy resin company, the brand name Efototo YDF-170 which is a product of Toto Kasei Co., Ltd. Toh YDF-175 "," Efototo YDF-2004 ", bisphenol F-type epoxy compounds, such as" Aral Daito XPY306 "by Asahi Kasei Chemicals, product name" EBPS-200 "which is a Japanese powder product, and brand name" EPX "by Asahi Denka Kogyo -30 ", bisphenol S epoxy compounds, such as a brand name" Epiclon EXA1514 "which are products of Nippon Ink Chemical Co., Ltd., bisphenols, such as a brand name" BPFG "which is a product of Osaka Gas Chemicals, Inc. Bixyrenol type or biphenyl type epoxy compounds, such as a brand name "YL-6056", "YL-6021", "YX-4000", "YX-4000H" which are orene type epoxy compounds and the Japan epoxy resin company, or Hydrogenated bisphenol-A epoxy compounds, such as such a mixture, the brand name "HBE-100" which is a Nippon-Shi Chemical company, the brand names "Efototo ST-2004", "ST-2007", "ST-3000" which are products of Toto Kasei Corporation, Product name `` Epicoat YL-903 '' which is a product made in Japan epoxy resin company, Product names `` Epicron 152 '' which is a product made in Japan ink chemical industry company, "Epikron 165", a product name "Efototo YDB-400" which is a product made by Toto Kasei Co., Ltd. Porto YDB-500, a brand name "D. E. R542 ", a canceled bisphenol A type epoxy compound, such as the brand name" AER8018 "by the Asahi Kasei Chemicals company, the brand name" Sumiepoxy ESB-400 "and" Sumiepoxy ESB-700 "by Sumitomo Chemical Industries, Ltd. Epoxy compound which has naphtharene skeletons such as brand names "ESN-190", "ESN-360" which are products of Tetsu Chemical company, brand names "HP-4032", "EXA-4700", "EXA-4750" which are products of Japan Ink Chemicals, Addition of ethylene oxides or propylene oxides such as aliphatic epoxy compounds such as "Eporite 400 E", "Eporite 400 P", "Eporite 1600" manufactured by Kyowa Chemical Co., Ltd., and the product name "Epolite 3002" manufactured by Kyoeisha Chemical Co., Ltd. Although bisphenol-A epoxy compound etc. are mentioned, It is not limited to these. These can be used individually or in combination of 2 or more types.

Of an acid anhydride (ai) and an unsaturated group-containing monoalcohol (a-ii) of a tribasic acid, a tetrabasic acid or a tribasic acid and a tetrabasic acid in the acid-modified epoxy (meth) acrylate compound (I). The method of reaction of the unsaturated-group-containing dicarboxylic acid compound which is a reaction product and the epoxy compound (a-iii) which has two epoxy groups in 1 molecule is first carried out in the carboxyl group and 1 molecule of said unsaturated-group-containing dicarboxylic acid compound. The epoxy group of the epoxy compound (a-iii) having two epoxy groups is reacted to obtain an epoxy compound (a) containing two unsaturated groups in one molecule represented by the general formula (1), followed by an unsaturated group-containing monocar The acid (b) is reacted, and the polybasic acid anhydride (c) is reacted thereon to obtain an acid-modified epoxy (meth) acrylate compound (I), but two of the carboxyl groups and one molecule of the dicarboxylic acid compound containing an unsaturated group Epoxy group When reacting with the epoxy group of the epoxy compound (a-iii) having, an unsaturated group-containing monocarboxylic acid (b) is added, and both reactions are carried out simultaneously, and then the polybasic acid anhydride (c) is further reacted to give an acid-modified epoxy (meth). Either method of obtaining an acrylate compound (I) may be sufficient.

2 in 1 molecule of an unsaturated group-containing dicarboxylic acid compound which is a reaction product of an acid anhydride (ai) of a tribasic acid or a tetrabasic acid or a tribasic acid and a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii) Reaction of the epoxy compound (a-iii) which has two epoxy groups has the following well-known catalyst and a polymerization inhibitor, and reaction temperature is 60-150 degreeC, in presence or absence of the diluent (IV) mentioned later, Preferably Preferably, it heats to 80-130 degreeC, and reacts in the presence of inert gas or air, and reaction time is in the range of 0.5-30 hours. If the reaction temperature is lower than 60 ° C, it is uneconomical because the reaction is required for a long time. On the other hand, if the reaction temperature is higher than 150 ° C, gelation may occur during the reaction. It should not be.

Further, an unsaturated group-containing dicarboxylic acid compound and one molecule which are a reaction product of the above-described tribasic acid, tetrabasic acid, or acid anhydride (ai) of tribasic acid and tetrabasic acid and unsaturated alcohol-containing monoalcohol (a-ii) The reactant of the epoxy compound (a-iii) having two epoxy groups in the reaction proceeds with the reaction of the carboxyl group of an unsaturated group-containing dicarboxylic acid compound with the epoxy group of the epoxy compound (a-iii) having two epoxy groups in one molecule. It is preferable to make it react as 5 mgKOH / g, preferably 1 mgKOH / g or less as an acid value of the said reactant, and to reduce as much as possible the carboxyl group emitted from the unsaturated carboxylic acid containing dicarboxylic acid. When the acid value is larger than 5 mgKOH / g, the range is set from the viewpoint that the stability of the photosensitive thermosetting resin composition and alkali developability may decrease.

Next, the unsaturated group-containing monocarboxylic acid (b) in the acid-modified epoxy (meth) acrylate compound (I) is a monocarboxylic acid showing radical polymerizability. For example, acrylic acid, methacrylic acid, Of adducts of 2-hydroxy ethyl (meth) acrylate and succinic anhydride, adducts of 2-hydroxy ethyl (meth) acrylate and phthalic anhydride, of 2-hydroxy ethyl (meth) acrylate and tetrahydro phthalic anhydride Adducts, adducts of 3-hydroxy propyl (meth) acrylate and succinic anhydride, adducts of 3-hydroxy propyl (meth) acrylate and phthalic anhydride, 3-hydroxy propyl (meth) acrylate and tetrahydro Adduct of phthalic anhydride, adduct of 4-hydroxy butyl (meth) acrylate and succinic anhydride, adduct of 4-hydroxy butyl (meth) acrylate and phthalic anhydride, 4-hydroxy butyl (meth) acrylic Adducts of rate and tetrahydro phthalic anhydride, adducts of trimethylpropane di (meth) acrylate and succinic anhydride, adducts of trimethylpropane di (meth) acrylate and phthalic anhydride, trimethylpropane di (meth) acrylate and tetra Adducts of hydrophthalic anhydride, adducts of pentaerythritol (tri) acrylate and succinic anhydride, adducts of pentaerythritol (tri) acrylate and phthalic anhydride, pentaerythritol (tri) acrylate and tetrahydro phthalic anhydride , Adducts of dipentaerythritol penta (meth) acrylate and succinic anhydride, adducts of dipentaerythritol penta (meth) acrylate and phthalic anhydride, dipentaerythritol penta (meth) acrylate and tetra Adduct of hydrophthalic anhydride, adduct of (meth) acrylic acid caprolactone adduct and succinic anhydride, ( Meta) acrylic acid caprolactone adducts and phthalic anhydride adducts; (meth) acrylic acid caprolactone adducts and tetrahydro phthalic anhydride adducts; (meth) acrylic acid esters and dibasic acid anhydride adducts; have. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group containing monocarboxylic acids (b) can be used individually or in combination of 2 or more types.

The unsaturated group containing epoxy compound (a) and unsaturated group containing monocarboxylic acid which have two epoxy groups in 1 molecule represented by the said General formula (1) in the said acid-modified epoxy (meth) acrylate compound (I) ( Compounding in reaction of b) is 0.8-1.5 equivalent of carboxyl group of unsaturated-group-containing monocarboxylic acid (b) with respect to 1 equivalent of epoxy group of the unsaturated-group-containing epoxy compound (a) which has two epoxy groups in 1 molecule. In the range, Preferably it is mix | blended in the range of 1.0-1.2 equivalent, More preferably, it is 1.0-1.05 equivalent. If the carboxyl group is less than 0.8 equivalent, there is a risk of causing gelation during the reaction. On the other hand, when it exceeds 1.5 equivalent, there exists a possibility that unreacted unsaturated group containing monocarboxylic acid (b) may remain in a large amount in acid-modified epoxy (meth) acrylate compound (I).

Unsaturated group-containing epoxy compound (a) and unsaturated group-containing monocarboxylic acid (b) having two epoxy groups in one molecule represented by General Formula (1) in the acid-modified epoxy (meth) acrylate compound (I). The reaction of the above) is a combination of the above, and a known polymerization inhibitor, which will be described later, is present, and in the presence or absence of the following diluent (IV), the reaction temperature is 60 to 150 ° C, preferably 80 to 130 It heats at C, and, in presence of air, reaction time is made to react in the range of 0.5-30 hours. When reaction temperature is lower than 60 degreeC, reaction is required for a long time and it is uneconomical and unpreferable. On the other hand, when higher than 150 degreeC, although there exists a possibility of gelatinizing during reaction, if gelatinization etc. can be prevented, it will not specifically limit.

In addition, the reactant of the unsaturated group-containing epoxy compound (a) and unsaturated group-containing monocarboxylic acid (b) having two epoxy groups in one molecule represented by the general formula (1) allows the epoxy group to react with the carboxyl group. The acid value of the reactants is preferably less than 10 mgKOH / g, preferably 5 mgKOH / g, more preferably 1 mgKOH / g or less, to reduce as much as possible the carboxyl group from the unsaturated group-containing monocarboxylic acid (b). When the acid value is larger than 10 mgKOH / g, the range is set from the viewpoint of lowering the stability and alkali developability of the photosensitive thermosetting resin composition.

Tribasic acid, tetrabasic acid, or acid anhydride (ai) of tribasic acid and tetrabasic acid and unsaturated group containing monoalcohol (a-ii) in manufacture of said acid-modified epoxy (meth) acrylate compound (I) In the reaction between the unsaturated group-containing dicarboxylic acid compound as the reaction product and the epoxy compound (a-iii) having two epoxy groups in one molecule, and in one molecule represented by the general formula (1) as the reaction product. In the reaction of two unsaturated group-containing epoxy compounds (a) and unsaturated group-containing monocarboxylic acids (b), it is preferable to use a well-known catalyst in order to advance reaction smoothly. Examples of such a catalyst include tertiary amines such as triethylamine and dimethyl benzyl amine or imidazole derivatives such as quaternary ammonium salts, imidazole and 2-methyl imidazole, and organophosphorus compounds such as triphenyl phosphine, and tri And organic antimony compounds such as phenyl antimony.

Such a catalyst is 100 parts by weight of the total of the tribasic acid, tetrabasic acid, or acid anhydride (ai) of tribasic acid and tetrabasic acid and unsaturated alcohol-containing monoalcohol (a-ii), and an unsaturated group which is the reaction product. 100 parts by weight in total of the containing dicarboxylic acid compound and the epoxy compound (a-iii) having two epoxy groups in one molecule, and an unsaturated group having two epoxy groups in one molecule represented by the general formula (1), the reaction product. Regarding the total of 100 parts by weight of the containing epoxy compound (a) and the unsaturated group-containing monocarboxylic acid (b), each can be used in the range of 0.01 to 10 parts by weight, preferably in the range of 0.05 to 5 parts by weight. In the case of less than 0.01, reaction may require a long time and may be uneconomical. On the other hand, when it exceeds 10 weight part, since reaction is too fast, temperature control is difficult, and when heat_generation | fever is high, there exists a possibility of gelatinization, but if gelatinization etc. can be prevented, it is not limited to this.

Reaction of the said tribasic acid, tetrabasic acid, or acid anhydride (ai) of a tribasic acid and a tetrabasic acid with an unsaturated group containing monoalcohol (a-ii), and the said unsaturated product containing dicarboxylic acid compound 1 Reaction of epoxy compound (a-iii) having two epoxy groups in a molecule, furthermore, epoxy compound (a) containing two unsaturated groups and monounsaturated monocarboxylic acid in one molecule represented by the above general formula (1) as the reaction product In the reaction of (b), a known polymerization inhibitor is used to ensure the stability during the reaction and the storage stability of the reaction product.

As such a polymerization inhibitor, for example, hydroquinone, monomethyl ether hydroquinone, toluhydroquinone, dit-4-methyl phenol, monomethyl ether hydroquinone, phenoxyazine, t-butylcatechol, etc. Can be mentioned. The amount used thereof is 100 parts by weight in total of the tribasic acid, tetrabasic acid or acid anhydride (ai) of tribasic acid and tetrabasic acid and the unsaturated group-containing monoalcohol (a-ii), and the reaction product is unsaturated. 100 parts by weight in total of the group-containing dicarboxylic acid compound and the epoxy compound (a-iii) having two epoxy groups in one molecule, and further, an unsaturated having two epoxy groups in one molecule represented by the general formula (1), the reaction product. It can be used in the range of 0.0001-1 weight part respectively, Preferably it is 0.001-0.5 weight part with respect to a total of 100 weight part of group containing epoxy compound (a) and unsaturated group containing monocarboxylic acid (b). When the amount is less than 0.0001 parts by weight, the polymerization inhibiting effect is small and gelation occurs during the reaction, whereby the target compound cannot be obtained, or there is a fear that the storage stability of the reaction product is significantly reduced. On the other hand, when it exceeds 1 weight part, the hardening reaction of the photosensitive thermosetting resin composition containing the said acid-modified epoxy (meth) acrylate compound (I) and the epoxy compound (II) which has two epoxy groups in 1 molecule is inhibited, The hardened | cured material containing an unhardened | cured material can be obtained, and there exists a possibility that it may not satisfy the required performance of each characteristic.

Acid-modified epoxy (meth) acrylate compound (I) of this invention is unsaturated group containing monocarboxylic acid in the unsaturated group containing epoxy compound (a) which has two epoxy groups in the specific 1 molecule obtained by said reaction. It is a polycarboxylic acid type epoxy (meth) acrylate compound which made polybasic acid anhydride (c) react with the secondary alcoholic hydroxyl group in the molecule | numerator of the reaction product obtained by making (b) react, and introduce | transduced the carboxyl group in the molecule | numerator.

Examples of the polybasic acid anhydride (c) include maleic anhydride, succinic anhydride, itaconic acid, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, and hexahydro. Acid anhydrides of dibasic acids such as phthalic anhydride, methyl hexahydro phthalic anhydride, nazixic anhydride, 3, 6-endmethylene tetrahydro phthalic anhydride, tetrabromo phthalic anhydride, and tribasic acids such as trimellitic anhydride, Pyromellitic anhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetra carboxylic dianhydride, butanetetra carboxylic dianhydride, benzophenone tetra carboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, ethylene glycol bis (Trimeric anhydride) ester, glycerin α, α-bis (trimellitic anhydride) ester β-monoacetic acid Tel, there may be mentioned acid anhydrides of tetrabasic acids such as naphthalene tetracarboxylic dianhydride. Among them, aliphatic or alicyclic compounds such as succinic anhydride, tetrahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride and methyl hexahydro phthalic anhydride in terms of protecting and maintaining the ink storage stability and developing life It is more preferable to select an acid anhydride of a dibasic acid having a structure. In addition, the said polybasic acid anhydride (d) can be used individually or in combination of 2 or more types.

In the present invention, the acid value of the acid-modified epoxy (meth) acrylate compound (I) may be in the range of 30 to 160 mgKOH / g, preferably in the range of 80 to 120 mgKOH / g, and an amount sufficient to satisfy the range of this acid value. Polybasic acid anhydride (c) is blended. When the acid value is less than 30 mgKOH / g, the solubility worsens with respect to the aqueous alkali solution, which is a developer, and the development of the formed film may be difficult, and the solder heat resistance, PCT resistance, and the like may be lowered. On the other hand, when it exceeds 160 mgKOH / g, unreacted polybasic acid anhydride (d) remains in an acid-modified epoxy (meth) acrylate compound, and it develops to the surface of an exposed part irrespective of exposure conditions in photocuring (temporary hardening). It may become.

In the production of the acid-modified epoxy (meth) acrylate (I) of the present invention, the unsaturated group-containing monocarbyl is contained in the unsaturated compound-containing epoxy compound (a) having two epoxy groups in one specific molecule obtained by the above reaction. The reaction is carried out by reacting the main acid (b) and reacting the polybasic acid anhydride (c) with the secondary alcoholic hydroxyl group of the reaction product thereon, but the reaction of reacting the polybasic acid anhydride (c) with the presence of the diluent (IV) described later. Under or without it, the reaction temperature is heated to 30 to 150 ° C, preferably 70 to 130 ° C, and preferably in the presence of air, the reaction time is reacted for 0.5 to 30 hours. When reaction temperature is lower than 30 degreeC, it requires a long time for reaction and it is uneconomical. On the other hand, when it is higher than 150 degreeC, although there exists a possibility of gelatinizing during reaction, if gelatinization etc. can be prevented, it is not limited to this. In addition, in reaction, the said well-known polymerization inhibitor and a catalyst can be added and used for the purpose of advancing reaction smoothly, or the objective of ensuring stability during reaction and storage stability of a reaction product.

As described above, the acid-modified epoxy (meth) acrylate compound of the present invention can be prepared by the following general formula,

Formula 31

(Wherein M is a hydrogen atom or

(Formula 32)

Wherein at least one of M

(Formula 33)

X is the same or different group selected from a divalent aromatic group, an alkyl group, a cyclohexyl group, Y is the same or different aromatic group selected from a trivalent or tetravalent aromatic group, and A is unsaturated Is a residue of a group-containing monoalcohol, Q is a residue of an unsaturated group-containing monocarboxylic acid, G represents a residue of a polybasic acid containing at least one hydrogen atom or at least one carboxyl group, at least one of G is a residue of a polybasic acid, and n is In the formula, X and Y are as described above, A represents the residue of the unsaturated group-containing monoalcohol described above, and Q represents the residue of the saturation group-containing monocarboxylic acid described above. , G represents a residue of the polybasic acid described above containing at least one hydrogen atom or at least one carboxyl group, and at least one of G is a residue of the polybasic acid. Therefore, what was demonstrated in the manufacturing method of the acid-modified epoxy (meth) acrylate compound of the said invention can be applied as it is.

Next, the acid-modified epoxy (meth) acrylate compound (I) which is 2nd invention of this invention, the epoxy compound (II) which has 2 or more epoxy groups in 1 molecule, a photoinitiator (III), and a diluent (IV) The photosensitive thermosetting resin composition to contain is demonstrated.

The epoxy compound (II) having two or more epoxy groups in one molecule constituting the photosensitive thermosetting resin composition is not particularly limited, but phenols, carboxylic acids, glycols, or amines having two or more active hydrogens in one molecule It can be obtained by epoxidizing to epichlorohydrin by a well-known method combining single or 2 types or more. In addition, phenols, carboxylic acids, glycols, or amines having two active hydrogens in one molecule are epoxidized to epichlorohydrin by a known method or a combination of two or more thereof. An epoxy compound having three or more epoxy groups in one molecule obtained by epoxidizing epichlorohydrin by a known method may be used. Further, in one molecule obtained by epoxidation of phenol novolac having three or more phenolic hydroxyl groups in one molecule obtained by formaldehyde addition condensation of phenols such as phenol and cresol by epichlorohydrin by a known method. The epoxy compound which has three or more epoxy groups can also be used.

General commercial items can also be used for the epoxy compound (II) which has two or more epoxy groups in the said one molecule. Although it does not specifically limit as a commercial item, For example, the brand names "Epicoat 828", "Epicoat 834", "Epicoat 1001", "Epicoat 1004" which are products of Japan epoxy resin company, "Epicoat 1004", a product made by Japan Ink Chemical Industries, Ltd. "Epicron 840", "Epicron 850", "Epicron 1050", "Epicron 2055", trade name "Efototo 128" manufactured by Toto Chemical Co., Ltd., trade name "D. E. R. 317, "D. E. R. 331, `` D. E. R. 661, "D. ER 664, product names `` AER 250 '', `` AER 260 '', `` AER 2600 '', products of `` Sumiepoxy ESA-011 '', `` Sumiepoxy ESA-014 '', `` Sumiepoxy ELA '', products manufactured by Asahi Kasei Chemicals Co., Ltd. Bisphenol A type epoxy compounds such as "-128", the brand name "Epiclon 830S" which is a product of Japan Ink Chemicals, the brand name "Epicoat 807" which is a product of Japan epoxy resin company, the brand name Efototo YDF-170 which is a product of Toto Kasei Co., Ltd., Bisphenol F type epoxy compounds, such as "Efototo YDF-175", "Efototo YF-2004", "Aral-Dato XPY 306" by Asahi Kasei Chemicals, the brand name "EBPS-200" which is a Japanese chemical company, Asahi Denka Bisphenol S type epoxy compounds, such as a brand name "EPX-30" which is an industrial company product, a brand name "Epiclon EXA 1514" which is a product of Nippon Ink Chemical Co., Ltd., and a brand name "BPFG" which is a product of Osaka Gas Chemicals, Inc. Bixyrenol type or biphenyl type epoxy compounds, such as a phenol fluorene type | mold epoxy compound and the brand names "YL-6056", "YL-6021", "YX-4000", and "YX-4000H" which are products of Japan epoxy resin company Hydrogenated bisphenol A-type epoxy, such as the brand name "Efototo ST-2004", "ST-2007", "ST-3000" which are products of Toto Kasei Co., Ltd., and brand name "HBE-100" which is a new Nippon Corp. product. Compound, brand name "Epicoat 152" which is a product made by Japan epoxy resin company, "Epicoat 154", brand name "DEN 431" which is a product made by Dow Chemical Company, "D. EN 438, brand name `` Epiron N-680 '', `` Epiron N-690 '', `` Epiron N-695 '', `` Epiron N-730 '', `` Epiron N-770 '' which are products of Japan Ink Chemicals Co., Ltd. , "Epicron N-865", brand name "Efototo YDCN-701" which is a product made by Toto Kasei Co., Ltd., "Epotto YDCN-704", brand name "AER 'ECN 1235" made by Asahi Kasei Chemicals, "AER' ECN 1273", "AER 'ECN 1299", "AER' XPY 307", the Japanese chemical company brand name "EPPN-201", "EOCN-1025", "EOCN-1020", "EOCN-104S", "RE-306", Sumitomo Chemical Phenolic novolac or cresol novolac-type epoxy compounds such as trade name "Sumiepoxy ESCN-195X", "ESCN-220" which are products of an industrial company, a brand name "Epicoat YL-903" which are products of Japan epoxy resin, Japan's ink chemical industry "Epicron 152", "Epicron 165", the brand name "Efototo YDB-400" which is made by Toto Kasei Co., Ltd., "Epot Sat YDB-500, a brand name "D. E. R 542 ", a canceled bisphenol A epoxy compound, such as the brand name" AER 8018 "by the Asahi Kasei Chemicals company, the brand names" Sumiepoxy ESB-400 "and" Sumiepoxy ESB-700 "by Sumitomo Chemical Industries, Ltd. , Epoxy having naphtharene skeletons such as brand name "ESN-190", "ESN-360" which are products of Shin-Nitetsu Chemical Co., Ltd., product name "HP-4032", "EXA-4700", "EXA-4750" which are products of Japan Ink Chemical Industries, Ltd. Compound, epoxy compound having indicator cropentagene skeletons such as "HP-7200" which are products of Nippon Ink Chemical Co., Ltd., "HP-7200H", brand name "YL-933" which is a product of Japan epoxy resin company, a Japanese chemical company Heterocyclic epoxidation, such as trishydroxy phenylmethane type epoxy compounds, such as "EPPN-501" and "EPPN-502", the brand name "TEPIC" by Nissan Chemical Co., Ltd., and the brand name "TGI" by Mitsubishi Gas Chemical Co., Ltd. Compound, brand name "Epicoat 604" which is a product made in Japan epoxy resin, brand name "Efototo YH-434" which is a product made by Toto Kasei Corporation, brand name "AER 'MY720" which is Asahi Kasei Chemicals company, brand name "Sumiepoxy ELM-120 made by Sumitomo Chemical Industries, Ltd. Glycidyl amine type epoxy compounds, such as Daicel Chemical Co., Ltd. product name "Cerokiside 2011", Asahi Kasei Chemicals company name "AER 'CY175", "AER' CY179 and other alicyclic epoxy compounds, Kyoeisha Chemical Co., Ltd. Aliphatic epoxy compounds, such as a brand name "Eporite 400E", "Eporite 400P", "Eporite 1600", bisphenol-A epoxy with addition of ethylene oxide or propylene oxide, such as brand name "Eporite 3002" by Kyoeisha Chemical Co., Ltd. Although a compound etc. are mentioned, It is not limited to these. These epoxy compounds can be used individually or in combination of 2 or more types.

Epoxy compound (II) which has two or more epoxy groups in the said 1 molecule heats and hardens after image formation of a resist pattern, and the carboxyl group and 1 molecule of an acid-modified epoxy (meth) acrylate compound (I) It reacts between the epoxy groups of the epoxy compound (II) which has two or more epoxy groups in it, and forms a strong bond, and improves characteristics, such as adhesiveness with the hardened film of a soldering resist and a base material, heat resistance, etc. The compounding quantity is 0.1-1.5 equivalent, preferably 0.1-1.5 equivalents of the epoxy group of the epoxy compound (II) which has two or more epoxy groups in 1 molecule with respect to 1 equivalent of the carboxyl group in the molecule | numerator of an acid-modified epoxy (meth) acrylate compound (I). It is 0.5 ~ 1. 3 equivalent, More preferably, it is mix | blended in the range of 1.0-1.2 equivalent. When less than 0.1 equivalent, the hygroscopicity of a cured film becomes high and there exists a possibility that electrical insulation may fall. On the other hand, when it exceeds 1.5 equivalent, ultraviolet-ray (light) hardenability (temporary hardening) and alkali developability fall, and there exists a possibility that image formation of a resist pattern may become difficult.

Next, the photoinitiator (III) in the photosensitive thermosetting resin composition of this invention is demonstrated in detail. The photoinitiator (III) used by this invention has a function which generate | occur | produces a radical by ultraviolet (light) irradiation and hardens | cures it by radical polymerization, when hardening | curing (temporarily hardening) the said photosensitive thermosetting resin composition by ultraviolet-ray (light). .

A well-known thing can be used as such a photoinitiator (III), As a preferable photoinitiator (III), benzoin and benzoin alkyl ether, such as benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc. are mentioned, for example. , Acetphenone, 2, 2-diethoxy-2-phenylacetphenone, 1, 1-dichloroacetphenone, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] Acetphenones such as 2-morpholinopropane-1-one and 2-benzyl-2-dimethyl amino-1- (4-morpholinophenyl) -butanone-1, N, N-dimethylamino acetphenone , Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone and 2-amino anthraquinone, thioxanthones such as 2 and 4-dimethyl thioxanthone, ketones such as acetphenone dimethyl ketar and benzyl dimethyl ketal Dehydration, benzophenone, methylbenzophenone, 4,4'-dichloro benzophenone, 4,4'-bisdiethyl aminobenzophenone, etc. Jope the like nonryu, and xanthan tonryu. These can be used individually or in combination of 2 or more types. Furthermore, such photoinitiator (III) is known, such as benzoic acid esters, such as ethyl-4-dimethylamino benzoate and 2- (dimethylamino) ethyl benzate, or tertiary amines, such as triethylamine and triethanolamine. May be used alone or in combination of two or more thereof.

It is preferable to use the usage-amount of said photoinitiator (III) in 0.1-30 weight part with respect to 100 weight part of acid-modified epoxy (meth) acrylate compounds (I), Furthermore, in the range of 1-20 weight part It is preferable to use. When it is less than 0.1 weight part, superposition | polymerization does not advance by ultraviolet (light) irradiation, but the formed film becomes uncured and there exists a possibility that alkali developability may fall. On the other hand, when it exceeds 30 weight part, there exists a possibility that the heat resistance and a mechanical characteristic of a cured film may fall.

Next, the diluent (IV) in the photosensitive thermosetting resin composition of this invention is demonstrated in detail.

As a diluent (IV) used for the photosensitive thermosetting resin composition of this invention, an organic solvent, (meth) acrylic acid ester, or a mixture thereof is mentioned, The said acid-modified epoxy (meth) acrylate compound (I) is melt | dissolved, As a solder resist ink, a diluent having an appropriate working viscosity and a reactivity such as (meth) acrylic acid ester is taken into the network during radical polymerization to improve photocurability, heat resistance, crack resistance, and adhesion to a substrate. It has a working effect.

In addition, a diluent (IV) is a tribasic acid at the time of obtaining the unsaturated compound containing epoxy compound (a) which has two epoxy groups in 1 molecule in manufacture of the said acid-modified epoxy (meth) acrylate compound (I), Reaction of a tetrabasic acid or an acid anhydride (ai) of a tribasic acid and a tetrabasic acid with an unsaturated group-containing monoalcohol (a-ii), and a dicarboxylic acid compound containing an unsaturated group which is the reaction product and two of one molecule Reaction of the epoxy compound (a-iii) which has an epoxy group, and reaction of the unsaturated group containing epoxy compound (a) and unsaturated group containing monocarboxylic acid (b) which have two epoxy groups in 1 molecule, and this reaction product and a polybasic acid In the reaction of the anhydride (c), it may be adjusted to an appropriate viscosity in the diluent (IV) for the purpose of obtaining a stable reaction product which does not cause gelation.

As such a diluent (IV), For example, ketones, such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons, such as toluene, xylene, and tetramethyl benzene, methyl cellosolve, butyl cellosolve, methyl carbitol, and butyl carbitol Glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate Alcohols such as ethanol, ethanol, propanol, ethylene glycol, propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and sorbents such as petroleum solvents such as naphtha. However, it is not limited to these. These can be used individually or in combination of 2 or more types.

In addition, a diluent (IV) can be used by replacing part or whole quantity of the said organic solvent with the (meth) acrylic acid ester which has radical polymerizability. As such (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, butyl (meth) acrylate, i-butyl (meth) acryl Alkyl (meth) acrylates, such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and glycidyl (meth) Amino alkyl (meth), such as epoxy group containing (meth) acrylates, such as acrylate, (meth) acrylamide, N, N-dimethyl amino ethyl (meth) acrylate, and N, N-diethyl amino ethyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, and the like. Amino alkyl (meth) acrylates such as mono or di (meth) acrylates of glycols, N, N-dimethyl (meth) acrylamides, N, N-dimethyl amino ethyl (meth) acrylates, hexanediol, Polyhydric alcohols such as trimetholpropane, pentaerythritol, ditrimethylpropane, dipentaerythritol, trishydroxy ethyl isocyanurate, or polyhydric (meth) acryl such as ethylene oxide or propylene oxide adduct (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as acrylates, phenoxy ethyl (meth) acrylates, and polyethoxydi (meth) acrylates of bisphenol A, glycerin diglycidyl ether and trimethyl (Meth) acrylates of glycidyl ethers such as propane triglycidyl ether and triglycidyl isocyanurate and ε-caprolactone modification Although epsilon -caprolactone modified (meth) acrylates, such as tris (acryloxyethyl) isocyanurate, a melamine (meth) acrylate, etc. are mentioned, It is not limited to these. These can be used individually or in combination of 2 or more types.

The usage-amount of the said diluent (IV) is mix | blended in the range of 1-300 weight part with respect to 100 weight part of acid-modified epoxy (meth) acrylate compounds (I). In addition, when using (meth) acrylic acid esters as said diluent (IV), the usage-amount is 3-50 weight part with respect to 100 weight part of said acid-modified epoxy (meth) acrylate compounds (I), Preferably it is used in the range of 5-15 weight part. When it is less than 3 weight part, the effect of providing photocurability may not be enough, and when it exceeds 50 weight part, there exists a possibility that the touch-drying property of a dry film may fall.

The photosensitive thermosetting resin composition of this invention has a carboxyl group in the molecule | numerator of the said acid-modified epoxy (meth) acrylate compound (I) in a thermosetting process (finishing hardening) as needed, and two or more epoxy groups in 1 molecule. A hardening accelerator can be added in order to accelerate reaction with an epoxy compound (I). As the curing accelerator, for example, imidazole, 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenyl imidazole and 1- (2-cyanoethyl) -2-ethyl-4-methyl imidazole, guanamines such as guanamine, aceto guanamine, and benzoguanamine, and dicyandi Amine compounds such as amide, benzyl dimethyl amine, 4- (dimethyl amino) -N, N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine, melamine and the like. These can be used individually or in combination of 2 or more types.

The usage-amount of such a hardening accelerator can be used in 0.1-10 weight part with respect to 100 weight part of said acid-modified epoxy (meth) acrylate compounds (I), Preferably it can be used in the range of 0.5-2 weight part. In the case of less than 0.1 part by weight, the effect of promoting the curing reaction of the epoxy compound (II) having two or more epoxy groups in one molecule becomes small, and in the case of more than 10 parts by weight, the life of the curable resin composition may be shortened. have.

An inorganic filler can be added to the photosensitive thermosetting resin composition of this invention for the purpose of improving adhesiveness with a printed wiring board as needed. For example, inorganic fillers such as talc, silica, barium sulfate, barium titanate, silicon oxide, aluminum oxide, calcium carbonate and aluminum hydroxide can be blended. These inorganic fillers can be added in the range of up to 150 weight part with respect to 100 weight part of photosensitive thermosetting resin compositions. When it exceeds 150 weight part, it will adversely affect sclerosis | hardenability, and the physical property of a cured film will fall.

To the photosensitive thermosetting resin composition of this invention, various coloring agents, leveling agents, antifoamers, etc. which are added to the normal soldering resist resin composition as needed in addition to the above component can be added.

The photosensitive thermosetting resin composition of this invention mixes the compounding component of (I), (II), (III), and (IV) which were mentioned above, and the compounding component added as needed uniformly with a roll mill, a sand mill, etc. Can be obtained. Moreover, application | coating on the printed wiring board of curable resin composition of this invention is normally performed by the screen printing method, the electrostatic coating method, the roll coater method, the curtain coater method, etc. After coating, it is dried for 10 to 60 minutes in the range of 60 to 90 ° C, and irradiated with active energy rays such as ultraviolet rays, and then unexposed to a rare alkali aqueous solution such as 0.1 to 5% by weight aqueous sodium carbonate solution. The solder pattern is then developed to remove an image of the solder pattern. After that, in order to completely cure the film, an epoxy compound (II) having two or more epoxy groups in one molecule, which is subjected to a heat treatment (5 to 60 minutes at 100 to 180 ° C.) as a final cure using a hot air dryer or far infrared rays or the like. When the (meth) acrylic acid ester is used as the acid-modified epoxy (meth) acrylate compound (I) and the diluent (IV) in addition to the curing reaction of the acid-modified epoxy (meth) acrylate compound (I), and (meth The polymerization of acrylic acid esters is accelerated | stimulated, and the cured film excellent in adhesiveness, heat resistance, and a mechanical characteristic can be obtained. Furthermore, if necessary, for example, by heating at a temperature of 140 to 180 ° C. and thermosetting, further, polymerization of the acid-modified epoxy (meth) acrylate compound (I) and the (meth) acrylic acid esters of the diluent (IV) is carried out. In order to accelerate | stimulate, the hardened film which has the outstanding characteristic can be obtained again by exposing by ultraviolet-ray (light) again.

As an irradiation light source for ultraviolet-ray curing, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples. This invention is not limited to the following Example. In the present embodiment, "parts" are parts by weight unless otherwise specified. In addition, in this Example, an acid-modified epoxy (meth) acrylate resin means that the acid-modified epoxy (meth) acrylate compound was diluted with the organic solvent, (meth) acrylic acid ester, or a mixture thereof.

Synthesis example of acid-modified epoxy acrylate resin

Synthesis Example  One

70 parts of trimellitic anhydride, 48 parts of 2-hydroxy ethyl acrylate, 0.5 parts of triphenyl phosphine, and 0.4 parts of monomethyl ether hydrokinone were placed in a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer. While blowing air, the mixture was heated while stirring to maintain the temperature at 85 to 95 ° C for reaction. The reaction was followed at IR and continued until the absorption of acid anhydride (1780 cm ⁻¹ ) indicating the presence of unreacted trimellitic anhydride was lost. The reaction required 6 hours. Subsequently, 311 parts of bisphenol-A epoxy compound (trade name "AER 260" by the Asahi Kasei Chemicals Co., Ltd. product) was put into it, heated with stirring to maintain the temperature at 110 to 120 ° C, and reacted for 4 hours. An unsaturated acid value of 0.1 mgKOH / g was obtained. A group containing epoxy compound was obtained. Thereafter, 62 parts of acrylic acid, 1.6 parts of triphenyl phosphine and 0.9 part of monomethyl ether hydrokinone were added thereto, and the mixture was heated with stirring to react for 15 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 0.2 mgKOH / g. . Then, 149 parts of tetrahydro phthalic anhydride were added, and it stirred for 10 hours, stirring, maintaining the temperature at 100-110 degreeC, and the acid-modified epoxy acrylate compound of the acid value 85 mgKOH / g was obtained. This acid-modified epoxy acrylate compound was diluted with 70 parts of absorbent naphtha and 280 parts of carbitol acetate to obtain an acid-modified epoxy acrylate resin (a-1) having a nonvolatile content of 65%.

Synthesis Example  2

Into a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, 79 parts of pyromellitic anhydride, 99 parts of 2-hydroxyethyl methacrylate, 0.5 part of triphenyl phosphine, and 0.4 part of monomethyl ether hydrokinone were added. For that purpose, 40 parts of acrylic acid was added for the purpose of lowering the viscosity of the reaction solution, and the mixture was heated under stirring while blowing air to maintain the temperature at 85 to 95 ° C for reaction. The reaction was followed at IR and continued until the absorption of acid anhydride (1780 cm ⁻¹ ) indicating the presence of unreacted pyromellitic anhydride was lost. The reaction required 10 hours. Next, 215 parts of bisphenol F-type epoxy compounds (trade name "Epiclon 830-S" manufactured by Nippon Ink Chemical Co., Ltd.), 1.6 parts of triphenyl phosphine and 0.9 part of monomethyl ether hydrokinone were added to further increase the viscosity of the reaction solution. For the purpose of lowering, 100 parts of carbitol acetate were added, and the mixture was heated under stirring to react for 17 hours while maintaining the temperature at 110 to 120 ° C. to obtain a reaction product having an acid value of 0.1 mgKOH / g in terms of solid content. Then, 163 parts of tetrahydro phthalic anhydride were added, and it stirred under stirring, keeping temperature at 100-110 degreeC for 10 hours, and obtained resin containing the acid-modified epoxy (meth) acrylate compound of acid value 100 mgKOH / g in conversion of solid content. The acid-modified epoxy (meth) acrylate resin was further diluted with 300 parts of carbitol acetate to obtain an acid-modified epoxy (meth) acrylate resin (a-2) having a nonvolatile content of 60%.

Synthesis Example  3

89 parts of pyromellitic anhydride, 124 parts of 4-hydroxy butyl acrylate, 0.6 parts of triphenyl phosphines, and 0.4 parts of monomethyl ether hydrokinone were put into a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer. The mixture was heated under stirring while blowing air to keep the temperature at 85 to 95 ° C for reaction. The reaction was followed at IR and continued until the absorption of acid anhydride (1780 cm ⁻¹ ) indicating the presence of unreacted pyromellitic anhydride was lost. The reaction required 6 hours. Next, 216 parts of bisphenol F-type epoxy compounds (trade name "Epiclon 830-S" manufactured by Nippon Ink Chemical Co., Ltd.) were added thereto, and the mixture was heated under stirring to maintain the temperature at 110 to 120 ° C for 4 hours to react. The acid value was 0.1 mgKOH. The unsaturated group containing epoxy compound of / g was obtained. Thereafter, 41 parts of methacrylic acid, 1.7 parts of triphenyl phosphine and 0.9 part of monomethyl ether hydrokinone were added thereto, and 100 parts of carbitol acetate was added thereto for the purpose of lowering the viscosity of the reaction solution, and the mixture was heated under stirring to give a temperature of 110 parts. The reaction was carried out for 18 hours while maintaining at ˜120 ° C. to obtain a reaction product having an acid value of 0.2 mgKOH / g in terms of solid content. Subsequently, 57 parts of tetrahydro phthalic anhydride and 65 parts of succinic anhydride were added, and the reaction was carried out for 10 hours while maintaining the temperature at 100 to 110 ° C under stirring to give an acid-modified epoxy (meth) acrylate compound having an acid value of 100 mgKOH / g in terms of solid content. The resin containing was obtained. The acid-modified epoxy (meth) acrylate resin was further diluted with 120 parts of absorbent naphtha and 180 parts of carbitol acetate to obtain an acid-modified epoxy (meth) acrylate resin (a-3) having a nonvolatile content of 60%.

compare Synthesis Example  One

373 parts of cresol novolak-type epoxy compound (trade name "Epiclon N-690" by Nippon Ink Chemical Co., Ltd.), 126 parts of acrylic acid, and triphenyl phosphine in a reaction vessel equipped with a gas introduction pipe, a stirring device, a cooling tube, and a thermometer. 2.5 parts and 1 part of monomethyl ether hydrokinone were added, and carbitol acetate 100 was added for the purpose of lowering the viscosity of the reaction solution, and it was heated under stirring while blowing in air, maintaining the temperature at 110 to 120 ° C. for 15 hours. The reaction product was obtained with a reaction product having an acid value of 0.1 mgKOH / g in terms of solid content. Then, 149 parts of tetrahydro phthalic anhydride were put, and it stirred for 10 hours, keeping temperature at 100-110 degreeC under stirring, and obtained resin containing the acid-modified epoxy acrylate compound of acid value 85 mgKOH / g in conversion of solid content. The acid-modified epoxy acrylate resin was further diluted with 140 parts of absorbent naphtha and 110 parts of carbitol acetate to obtain an acid-modified epoxy acrylate resin (b-1) having a nonvolatile content of 65%.

compare Synthesis Example  2

309 parts of cresol novolak-type epoxy compound (trade name "Epicron N-690" by Nippon Ink Chemical Co., Ltd.), 42 parts of naphthol, and triphenyl phosphine in the reaction container provided with a gas introduction pipe, a stirring apparatus, a cooling tube, and a thermometer. 1.8 parts was added, while nitrogen was blown, the mixture was heated under stirring to react for 2 hours while maintaining the temperature at 140 to 150 ° C., followed by 83 parts of acrylic acid, 1.2 parts of triphenyl phosphine and 1.2 parts of monomethyl ether hydrokinone, and thereon In order to lower the viscosity of the reaction solution, 100 parts of carbitol acetate were added, and air was blown while maintaining the temperature at 110-120 ° C. under stirring to react for 13 hours to obtain a reaction product having an acid value of 0.2 mgKOH / g in terms of solid content. Then, 162 parts of tetrahydro phthalic anhydride were added, it was made to react under stirring, keeping temperature at 100-110 degreeC for 10 hours, and the resin containing the acid-modified epoxy acrylate compound of acid value 100 mgKOH / g in conversion of solid content was obtained. The acid-modified epoxy acrylate resin was further diluted with 300 parts of carbitol acetate to obtain an acid-modified epoxy acrylate resin (b-2) having a nonvolatile content of 60%.

compare Synthesis Example  3

Into a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, 338 parts of a naphthylene-modified bisphenol A epoxy compound, 98 parts of acrylic acid, 2.2 parts of triphenyl phosphine, and 0.9 parts of monomethyl ether hydrokinone were added. While blowing, the mixture was heated under stirring to maintain the temperature at 110 to 120 ° C. for 9 hours to obtain a reaction product having an acid value of 0.2 mg KOH / g. Subsequently, 162 parts of tetrahydro phthalic anhydride were put and reacted for 10 hours, keeping the temperature at 100-110 degreeC under stirring, and the acid-modified epoxy acrylate compound of the acid value 100 mgKOH / g was obtained. This acid-modified epoxy acrylate compound was diluted with 400 parts of propylene glycol monomethyl ether acetate to obtain an acid-modified epoxy acrylate resin (b-3) having a nonvolatile content of 60%.

Preparation of Photosensitive Thermosetting Resin Composition

Examples 1-3 and Comparative Examples 1-3

Resin (a-1-a-3, b-1-b-3) containing the acid-modified epoxy (meth) acrylate compound (I) obtained by said synthesis examples 1-3 and comparative synthesis examples 1-3 is used By mixing in the composition of Table 1 to prepare a photosensitive thermosetting resin composition.

The epoxy compound (II) which has two or more epoxy groups in 1 molecule in the said photosensitive thermosetting resin composition is a bisphenol-A epoxy compound (Brand name "AER 260" by the Asahi Chemicals Co., Ltd. product), and photoinitiator (III) is 2-methyl. -1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name "Irgacua 907" manufactured by Chiba Specialty Chemicals), and diluent (IV) Metyrolpropane triacrylate was used. In addition, dicyandiamide was used as other hardening accelerator, the brand name "BYK-A555" by BYK Chemi Corporation, and the brand name "phthalocyanine green" by Daiichi Seika Co., Ltd. were used for the pigment.

Evaluation of each photosensitive thermosetting resin composition of Table 1 was performed about the item described below, and the evaluation result was shown in Table 2.

(1) dry touch

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, the board | substrate was removed from the drying furnace and cooled to room temperature, and the touch drying property of the coating film was investigated. The judgment criteria are as follows.

○: There is no wrinkle, △: There is no wrinkle, but fingerprint is thin, ×: There is wrinkle

(2) alkali developability

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 20, 30, 40, 50, 60, 70 minutes in 80 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace, cooled to room temperature, and developed at 30 ° C. in a 1% by weight aqueous solution of sodium carbonate for 60 seconds under the condition of a spray pressure of 0.2 MPa, and visually confirmed the presence or absence of the development remaining in the dry coating film. It was. Judgment criteria are as follows.

(Circle): It is fully developed, (triangle | delta): Some coating film remains, x: Coating film remains completely

(3) sensitivity

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Subsequently, the substrate was taken out of the drying furnace and cooled to room temperature, and a step tablet (Kodak No. 2, all 21 stages) was placed on the coating film, and the ultraviolet light accumulated light amount 600mJ was used as a light source using a metal helide lamp (350 nm) under reduced pressure. After exposing on the condition of / cm ² and removing the step tablet, a 30% 1 wt% sodium carbonate aqueous solution was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the number of remaining coatings was visually determined by eye. Sensitivity was evaluated. The larger the number, the higher the sensitivity in the ultraviolet.

(4) adhesion

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, the board | substrate was taken out from the drying furnace, it cooled to room temperature, and the metal helide lamp (350 nm) was exposed as the light source on condition of 600mJ / cm <^2> of ultraviolet-light accumulated light under a reduced pressure, and it thermosetted for 60 minutes in the 150 degreeC hot-air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. The adhesiveness of the obtained cured coating film was evaluated in accordance with JIS D0202. The judgment criteria are as follows.

○: The number of checkerboard eyes 100 remains completely, △: The number of checkerboard eyes less than 100 The remaining 60 or more, X: The number of checkerboard snows remained only less than 60

(5) pencil hardness

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, the board | substrate was taken out from the drying furnace, it cooled to room temperature, and the metal helide lamp (350 nm) was exposed as the light source on condition of 600mJ / cm <^2> of ultraviolet-light accumulated light under a reduced pressure, and it thermosetted for 60 minutes in the 150 degreeC hot-air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. The pencil hardness of the obtained cured coating film was evaluated in accordance with JIS D0202.

(6) solder heat resistance

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, the board | substrate was taken out from the drying furnace, it cooled to room temperature, and the metal helide lamp (350 nm) was exposed as the light source on condition of 600mJ / cm <^2> of ultraviolet-light accumulated light under a reduced pressure, and it thermosetted for 60 minutes in the 150 degreeC hot-air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. The obtained cured coating film was immersed in the solder bath temperature-controlled at 260 degreeC for 10 second, and it repeated 5 times in total by performing the test which evaluates a coating-film state once. The judgment criteria are as follows.

○: No swelling, peeling, discoloration, △: Some swelling, peeling, discoloration has occurred, ×: Most swelling, peeling, discoloration has occurred

(7) Resistance to Pressure Cooker Test (PCT)

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, the board | substrate was taken out from the drying furnace, it cooled to room temperature, the metal helide lamp (350 nm) was exposed to the ultraviolet light accumulated amount of 600mJ / cm <^2> as a light source under reduced pressure, and it thermosetted for 60 minutes in the 150 degreeC hot-air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. PCT resistance of the obtained cured coating film evaluated the coating film state visually after exposing a coating film continuously for 50 hours on condition of 121 degreeC, 100% RH, and 2 atmospheres. Evaluation criteria are as follows.

○: No swelling, peeling, discoloration, △: Some swelling, peeling, discoloration has occurred, ×: Most swelling, peeling, discoloration has occurred

(8) cold heat cycle test

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Then, after removing a board | substrate from a drying furnace and cooling to room temperature, the metal helide lamp was exposed to the ultraviolet light accumulated light quantity of 600mJ / cm <^2> as a light source under reduced pressure, and it thermosetted for 60 minutes in the 150 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. In the cold heat cycle test, a test for continuously exposing the obtained cured coating film for 30 minutes under the condition of -65 ° C and then for 30 minutes under the condition of 125 ° C was performed as one cycle. The presence of cracks in the coating film was evaluated by eyes and an optical microscope.

○: There is no crack generation and peeling off, X: There is any or all of crack generation or peeling off

(9) Electroless Gold Plating Resistance Test

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace, cooled to room temperature, the negative film on which the solder resist pattern was drawn was applied to the coating film, and the metal helide lamp (350 nm) was exposed under a reduced pressure under a condition of 600mJ / cm ² of ultraviolet light accumulated as a light source, The 30 degreeC 1 weight% sodium carbonate aqueous solution was developed for 60 second on the conditions of the spray pressure of 0.2 MPa, pure water of room temperature was sprayed on the coating film for 60 second, and it wash | cleaned with water. Washing with this water was performed twice. Then, it thermosetted for 60 minutes in the 150 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. The electroless gold plating resistance test is performed by using a commercially available electroless nickel plating solution and an electroless gold plating solution on a substrate on which a cured coating film drawn with the obtained solder resist pattern is obtained. The thickness of the nickel plating layer is 5 μm and the thickness of the gold plating layer is 0.03 μm. The electroless plating was performed under the conditions of the following, and the coating film was peeled off according to JIS D0202, and the depth of plating was evaluated. Evaluation criteria are as follows.

(Circle): Peeling | coating to a coating film and the depth permeation of plating are not recognized, (triangle | delta): Peeling to a coating film is recognized very little and plating depth permeation is recognized, ×: The coating film peels completely.

(10) Electroless Tin Plating Resistance Test

Each photosensitive thermosetting resin composition of Table 1 was apply | coated completely by the screen printing method on the board | substrate with copper foil, and it dried for 30 minutes by 80 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace, cooled to room temperature, the negative film on which the solder resist pattern was drawn was applied to the coating film, and the metal helide lamp (350 nm) was exposed under a reduced pressure under a condition of 600mJ / cm ² of ultraviolet light accumulated as a light source, The 30 degreeC 1 weight% sodium carbonate aqueous solution was developed for 60 second on the conditions of the spray pressure of 0.2 MPa, pure water of room temperature was sprayed on the coating film for 60 second, and it wash | cleaned with water. Washing with this water was performed twice. Then, it thermosetted for 60 minutes in the 150 degreeC hot air drying furnace. Thereafter, the substrate was taken out of the drying furnace and cooled to room temperature. The electroless tin plating resistance test is performed by acidic degreasing, soft etching, and sulfuric acid treatment as a pretreatment of a substrate on which a cured coating film drawn with the obtained solder resist pattern is formed, and using a commercially available electroless tin plating solution. Electroless tin plating was performed on 70 degreeC and the conditions for 12 minutes so that the thickness of a plating layer might be 1 micrometer, and the state which peeled off a coating film according to JISD0202, and the depth of plating were evaluated. Evaluation criteria are as follows.

(Circle): Peeling | coating to a coating film and the depth permeation of plating are not recognized, (triangle | delta): Peeling to a coating film is recognized very little and plating depth permeation is recognized, ×: The coating film peels completely.

Photosensitive thermosetting resin composition Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Acid-modified epoxy (meth) acrylate resins (* 1) a-1 (65% of non volatile matter) 153.8 a-2 (60% of non volatile matter) 166.7 a-3 (60% of non volatile matter) 166.7 b-1 (65% nonvolatile matter) 153.8 b-2 (60% nonvolatile matter) 166.7 b-3 (60% nonvolatile matter) 166.7 Epoxy Compound (II) (* 2) 31.5 33.7 33.7 31.5 33.7 33.7 Photoinitiator (III) (* 3) 10 10 10 10 10 10 Diluent (IV) (* 4) 5 5 5 5 5 5 etc  Curing accelerator (* 5) 0.5 0.5 0.5 0.5 0.5 0.5  Antifoam (* 6) 1.9 2 2 1.9 2 2  Pigment (* 7) 0.9 One One 0.9 One One

The unit is parts by weight.

(* 1) diluted acid-modified epoxy (meth) acrylate compound (I) with the organic solvent.

(* 2) is brand name "AER260" made by Asahi Kasei Chemicals company.

(* 3) is brand name "irgacua 907" which is product of Chiba specialty chemicals company.

(* 4) is trimetholpropane triacrylate.

(* 5) is dicyandiamide.

(* 6) is brand name "BYK-A555" which is a BYK chemistry company.

(* 7) is brand name "phthalocyanine green" which is Daiichi Seika Industries Co., Ltd. product.

Evaluation item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Dry touch ○ ○ ○ ○ ○ ○ Alkali developability   Drying time 20 minutes ○ ○ ○ ○ ○ ○ 30 minutes ○ ○ ○ ○ ○ ○ 40 minutes ○ ○ ○ ○ △ ○ 50 minutes ○ ○ ○ ○ × ○ 60 minutes ○ △ △ ○ × △ 70 minutes △ × × △ × × Sensitivity Sweet 12 11 11 11 8 9 Adhesion ○ ○ ○ ○ × ○ Pencil hardness 7H 6H 6H 7H 4H 5H Solder heat resistance ○ ○ ○ ○ △ ○ PCT immunity ○ ○ ○ × ○ ○ Cold cycle resistance ○ ○ ○ × ○ ○ Gold plating resistance ○ ○ ○ × × ○ Tin plating resistance ○ ○ ○ × × ×

As can be clearly seen from the results in Table 2, the photosensitive thermosetting resin composition containing the acid-modified epoxy (meth) acrylate compound of the present invention has a balance of touch dryness, alkali developability, development life, and sensitivity. In addition, a cured coating film having excellent adhesion, hardness, solder heat resistance, PCT resistance, cold cycle resistance, and excellent gold plating resistance and tin plating resistance can be provided. On the other hand, the resin composition of the comparative example was unable to satisfy each evaluation balance.

(1) In the present invention, the acid-modified epoxy (meth) acrylate compound (I) has a photosensitive double bond and a carboxyl group which can be radically polymerized in a molecule, and is radically polymerized by a photopolymerization initiator under ultraviolet (light) irradiation. To form a cured product (temporary curing), and the part not irradiated with ultraviolet light (light) is excellent in the ability to be removed by a rare alkali solution, and furthermore, the carboxyl groups present in the cured product coexist in a thermosetting process (main curing). By reacting with the epoxy compound (II) to form a strong bond can be obtained an excellent cured coating.

(2) The photosensitive thermosetting resin composition containing the acid-modified epoxy (meth) acrylate compound of the present invention is excellent in the balance of dry touch, alkali developability and sensitivity, and high in adhesion, solder heat resistance, and PCT resistance required as a resist coating. It can provide a good level of cured coating, and also provide excellent gold plating resistance and tin plating resistance. For this reason, it is most suitable as a material for the manufacture of printed wiring boards, particularly for IC packages such as BGA (ball grid array) and CSP (chip scale package).

Claims (5)

An acid-modified epoxy (meth) acrylate compound represented by the following formula (1). (Formula 1)

(Wherein M is a hydrogen atom or (Formula 2)

Wherein at least one of M (Formula 3)

X is the same or different groups selected from divalent aromatic, alkyl and cyclohexyl groups, and Y is the same or different aromatics selected from trivalent or tetravalent aromatic groups A is a residue of an unsaturated group-containing monoalcohol, Q is a residue of an unsaturated group-containing monocarboxylic acid, G represents a residue of a polybasic acid containing at least one hydrogen atom or at least one carboxyl group, and at least one of G is Is a residue of a polybasic acid, n is an integer from 1 to 100.) A polybasic acid anhydride (c) is reacted with a reaction product obtained by reacting an unsaturated compound-containing epoxy compound (a) having two epoxy groups and a unsaturated group-containing monocarboxylic acid (b) in one molecule represented by the following formula (4). The manufacturing method of the acid-modified epoxy (meth) acrylate compound of Claim 1 which is used. (Formula 4)

(Wherein M is a hydrogen atom or (Formula 5)

Wherein at least one of M (Formula 6)

X is the same or different groups selected from divalent aromatic, alkyl and cyclohexyl groups, and Y is the same or different aromatics selected from trivalent or tetravalent aromatic groups A is a residue of an unsaturated group-containing monoalcohol, and n is an integer of 1 to 100.) The unsaturated group-containing epoxy compound (a) according to claim 2, wherein the unsaturated group-containing epoxy compound (a) having two epoxy groups in one molecule is a monobasic acid, a tetrabasic acid, or an acid anhydride (ai) of a tribasic acid and a tetrabasic acid and an unsaturated group-containing mono The acid-modified epoxy according to claim 1, which is obtained by reacting an epoxy group (a-iii) having two epoxy groups in one molecule with an unsaturated group-containing dicarboxylic acid compound obtained by reacting an alcohol (a-ii). The manufacturing method of a (meth) acrylate compound. Epoxy group of epoxy compound (II) which has two or more epoxy groups in 1 molecule per 1 equivalent of carboxyl groups of acid-modified epoxy (meth) acrylate compound (I) of Claim 1, and acid-modified epoxy (meth) acrylate compound (I) 0.1-30 parts by weight of photopolymerization initiator (III) per 100 parts by weight of an epoxy compound (II) and an acid-modified epoxy (meth) acrylate compound (I) having 1 or more epoxy groups in an amount of 0.1-1.5 equivalents And 1 to 300 parts by weight of diluent (IV) per 100 parts by weight of the acid-modified epoxy (meth) acrylate compound (I) as essential components. Hardened | cured material obtained by hardening | curing the photosensitive thermosetting resin composition of Claim 4.