JP2005300785A - Photosetting/thermosetting resin composition and cured film of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting/thermosetting resin composition developable with an aqueous alkali solution, having low hydrolyzability, excellent in solder thermal resistance, chemical resistance, adhesion, electric insulation, etc., free from halogen, and having stable flame retardancy, and suitable for use in a tape carrier and a flexible printed wiring board, excellent in bending resistance, and ensuring little warpage after curing, and to provide a cured film of the composition. <P>SOLUTION: The photosetting/thermosetting resin compositions contain (A) a carboxylic resin containing one or more carboxyl groups per molecule, (B) a compound having two or more ethylenically unsaturated bonds per molecule, (C) a photopolymerization initiator, (D) a phosphoric acid amide compound represented by formula (I), and (E) a compound having one or more oxirane rings and/or oxetane rings per molecule. In the formula, R<SP>1</SP>and R<SP>2</SP>are the same or different and each represents H or a 1-4C alkyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a halogen-free and flame-retardant photocurable / thermosetting resin composition useful for the production of printed wiring boards. More specifically, as a solder resist used for a printed wiring board, a semiconductor carrier tape or COF (Chip on Film) used for TAB (Tape Automated Bonding), CSP (Chip Size Package), TCP (Tape Carrier Package), etc. Low hydrolyzability useful as a solder resist for flexible printed wiring boards, excellent solder heat resistance, chemical resistance, adhesion, electrical insulation, etc., developable with halogen-free, stable flame retardant alkaline aqueous solution The present invention relates to a photocurable / thermosetting resin composition and a cured coating film thereof.

  In general, as a solder resist for printed wiring boards, from the viewpoint of high accuracy and high density, there is a liquid development type solder resist that forms an image by developing after ultraviolet irradiation and is finally cured (main curing) by heat and light irradiation. Widely used. In particular, from the viewpoint of environmental issues, an alkali development type liquid solder resist using a dilute alkaline aqueous solution as a developing solution has become the mainstream.

As such an alkali development type solder resist, for example, a photosensitive resin obtained by adding a saturated or unsaturated polybasic acid anhydride to a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid, photopolymerization initiation A solder resist composition comprising an agent, a diluent and an epoxy compound has been proposed (see Patent Document 1).
As a method for imparting flame retardancy to such a solder resist composition, there are generally a method of blending a bromine compound, a method of blending a phosphate ester as a flame retardant, a method of blending red phosphorus, and the like. However, even if a brominated epoxy resin is used as an epoxy compound to be blended in the above composition as a thermosetting component, the bromine content is low and sufficient flame retardancy cannot be obtained. Moreover, although the method of using brominated phenol novolak type epoxy resin for the raw material of the said photosensitive resin can also be considered, there exists a problem that it cannot respond to halogen-free.
Next, the method of compounding the phosphate ester is that the phosphate ester is hydrolyzed by alkali development treatment or plating treatment at the time of manufacturing the printed wiring board, and the coating properties such as electrical insulation and electrocorrosion are deteriorated. There is a problem. In addition, the method of blending red phosphorus has a problem of appearance defects such as coloring due to red phosphorus and a decrease in sensitivity, and also has a problem of being subject to regulations such as the Fire Service Act for the storage of solder resist compositions. .

In addition, when such a composition is used for a tape carrier or a flexible printed wiring board, the bending resistance is poor and the amount of warping after curing is large. There is a problem that it is easy to cause sexual deterioration. On the other hand, a solder resist composition comprising a photosensitive resin in which an acid anhydride is added to a reaction product of a bisphenol F (or A) type polyfunctional epoxy compound and an unsaturated monocarboxylic acid has been proposed (Patent Literature). 2).
Thus, by using a linear polyfunctional epoxy resin as a raw material, the bending resistance and the amount of warping after curing are improved. A composition using an epoxy compound containing bromine in the main skeleton as a raw material has also been proposed. However, at present, the bromine content is low and sufficient flame retardancy is not obtained. Furthermore, such a flame retardant composition has a problem that it cannot cope with halogen-free.

In addition, halogen-free and flame-retardant photocurable / thermosetting compositions are obtained by reacting a polyfunctional epoxy compound with a phosphorus compound such as an unsaturated monocarboxylic acid and diphenylphosphinic acid, A composition containing a resin compound to which an acid anhydride has been added has been proposed (see Patent Document 3).
However, a resin obtained by reacting a polyfunctional epoxy compound with a phosphorus compound is difficult to increase the phosphorus content because of the molecular weight of the phosphorus compound to be introduced, and the problem that sufficient flame retardancy cannot be obtained. There is a problem that it has degradability.
JP 61-243869 (Claims) JP-A-5-32746 (Claims) JP 2000-327742 A (Claims)

Therefore, the present invention has been made to solve the above problems of the prior art, and its main purpose is low hydrolysis, solder heat resistance, chemical resistance, adhesion, electrical insulation, etc. It is to provide a photocurable / thermosetting resin composition that can be developed with an alkaline aqueous solution having excellent halogen-free and stable flame retardancy, and is further suitable for use in tape carriers and flexible printed wiring boards. An object of the present invention is to provide a photocurable / thermosetting resin composition that is excellent in flexibility and developable with an alkaline aqueous solution with little warping after curing.
Another object of the present invention is to have low hydrolyzability obtained by curing the photocurable / thermosetting resin composition by irradiation with active energy rays and / or heating, solder heat resistance, chemical resistance, adhesion. An object of the present invention is to provide a cured coating film that is excellent in properties, electrical insulation properties, and the like, is halogen-free and has stable flame retardancy.

As a result of intensive studies to achieve the above object, the inventors have (A) a carboxyl group-containing resin containing one or more carboxyl groups in one molecule,
(B) a compound having one or more ethylenically unsaturated bonds in one molecule;
(C) a photopolymerization initiator,
(D) a phosphoric acid amide compound represented by the following general formula (I):

（式中、Ｒ^１，Ｒ^２は、同一又は異なるもので、水素原子又は炭素数１〜４のアルキル基を表わす。）

及び（Ｅ）一分子中に１個以上のオキシラン環及び／又はオキセタン環を有する化合物を含有する光硬化性・熱硬化性樹脂組成物が、アルカリ水溶液により現像可能で、加水分解性が低く、はんだ耐熱性、耐薬品性、密着性、電気絶縁性等に優れ、ハロゲンフリーで安定した難燃性を有することを見出し、本発明を完成するに至った。
即ち、（Ａ）一分子中に１個以上のカルボキシル基を含有するカルボキシル基含有樹脂、（Ｂ）一分子中に１個以上のエチレン性不飽和結合を有する化合物、（Ｃ）光重合開始剤、及び（Ｅ）一分子中に１個以上のオキシラン環及び／又はオキセタン環を有する化合物を含有するアルカリ水溶液により現像可能な光硬化性・熱硬化性樹脂組成物に、上記一般式（Ｉ）で表わされるリン酸アミドを配合することにより、加水分解性が低く、はんだ耐熱性、耐薬品性、密着性、電気絶縁性等に優れ、ハロゲンフリーで安定した難燃性を付与することができることを見出した。上記一般式（Ｉ）で表わされるリン酸アミドは、リン酸エステルなどに比べ、著しく加水分解性が低く、又融点も高いため、プリント配線板製造時の加熱処理で融け出すことも無く、ハロゲフリーで安定した難燃性を付与することができる。

(In formula, R < ¹ >, R < ² > is the same or different, and represents a hydrogen atom or a C1-C4 alkyl group.)

And (E) a photocurable / thermosetting resin composition containing a compound having one or more oxirane rings and / or oxetane rings in one molecule is developable with an alkaline aqueous solution, has low hydrolyzability, The present inventors have found that it has excellent solder heat resistance, chemical resistance, adhesion, electrical insulation, etc., has halogen-free and stable flame retardancy, and has completed the present invention.
(A) a carboxyl group-containing resin containing one or more carboxyl groups in one molecule, (B) a compound having one or more ethylenically unsaturated bonds in one molecule, (C) a photopolymerization initiator And (E) a photocurable thermosetting resin composition that can be developed with an aqueous alkaline solution containing a compound having one or more oxirane rings and / or oxetane rings in one molecule. By blending the phosphoric acid amide represented by the formula, the hydrolyzability is low, the solder heat resistance, chemical resistance, adhesion, electrical insulation, etc. are excellent, and halogen-free and stable flame retardancy can be imparted. I found. The phosphoric acid amide represented by the above general formula (I) is significantly less hydrolyzable and has a higher melting point than phosphoric acid esters and the like, so it does not melt out by heat treatment during printed wiring board production, and is halogen free. Can provide stable flame retardancy.

  By using the photocurable / thermosetting resin composition of the present invention, it does not generate environmentally destructive substances such as dioxins, has low hydrolyzability, solder heat resistance, chemical resistance, adhesion, and electrical insulation. It is possible to provide a printed wiring board that is excellent in, for example, halogen-free and has stable flame retardancy. In particular, it has excellent PCT resistance and bending resistance, which is suitably used for semiconductor printed tapes such as TAB, CSP, and TCP, and flexible printed wiring boards such as COF, and has a highly reliable cured product (coating film) with little warpage. A flexible printed wiring board can be provided.

As a first aspect of the present invention, (A) a carboxyl group-containing resin containing one or more carboxyl groups in one molecule,
(B) a compound having one or more ethylenically unsaturated bonds in one molecule;
(C) a photopolymerization initiator,
(D) a phosphoric acid amide compound represented by the following general formula (I):

（式中、Ｒ^１，Ｒ^２は、同一又は異なるもので、水素原子又は炭素数１〜４のアルキル基を表わす。）

及び（Ｅ）一分子中に１個以上のオキシラン環及び／又はオキセタン環を有する化合物を含有することを特徴とするアルカリ水溶液により現像可能な光硬化性・熱硬化性樹脂組成物が提供される。好ましい態様としては、前記カルボキシル基含有樹脂（Ａ）が、さらに（Ａ’）一分子中に２個以上のエチレン性不飽和結合を有するカルボキシル基含有感光性樹脂であり、より好ましくは、下記一般式（II）、下記一般式（III）、及び下記一般式（Ｖ）で表わされる化合物からなる群から選ばれる少なくとも１種の多官能エポキシ化合物（ａ）

(In formula, R < ¹ >, R < ² > is the same or different, and represents a hydrogen atom or a C1-C4 alkyl group.)

And (E) a photocurable / thermosetting resin composition developable with an aqueous alkaline solution, comprising a compound having one or more oxirane rings and / or oxetane rings in one molecule. . As a preferred embodiment, the carboxyl group-containing resin (A) is a carboxyl group-containing photosensitive resin further having (A ′) two or more ethylenically unsaturated bonds in one molecule, and more preferably At least one polyfunctional epoxy compound (a) selected from the group consisting of compounds represented by formula (II), general formula (III) below, and general formula (V) below

（式中、Ｒ^３、Ｒ^４は、水素原子又はメチル基を表わし、Ｒ^５は、水素原子又はグリシジル基を表わし、ｎは、１〜５０の値を表わす。）

(In the formula, R ³ and R ⁴ represent a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a glycidyl group, and n represents a value of 1 to 50.)

（式中、Ｍは、下記一般式（IV）で示される基を表わし、Ｒ^６は、脂肪族又は芳香族多官能カルボン酸の残基を表わし、ｍは、１〜５０の値を表わす。）

(In the formula, M represents a group represented by the following general formula (IV), R ⁶ represents a residue of an aliphatic or aromatic polyfunctional carboxylic acid, and m represents a value of 1 to 50. )

（式中、Ｒ^７，Ｒ^８は、２価のシクロヘキサン環及び／又はベンゼン環を表わし、Ｒ^９，Ｒ^１０は、水素原子又はメチル基を表わし、Ｒ^１１は、水素原子又はグリシジル基を表わし、ｋは、０〜２５の値を表わす。）

(In the formula, R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, and R ¹¹ represents a hydrogen atom or a glycidyl group. , K represents a value from 0 to 25.)

（式中、ＸとＹは互いに異なる２価の芳香環を表わし、Ｇはグリシジル基及び／又は水素原子を表わし、ｐは、１〜２０の整数を表わす。）

と、不飽和モノカルボン酸（ｂ）との反応物に、飽和及び／又は不飽和多塩基酸無水物（ｃ）を反応させて得られるカルボキシル基含有感光性樹脂（Ａ’）である。
更に、別の態様として、前記光硬化性・熱硬化性樹脂組成物を、活性エネルギー線照射及び／又は加熱により硬化させて得られることを特徴とする硬化塗膜が提供される。

(In the formula, X and Y represent different divalent aromatic rings, G represents a glycidyl group and / or a hydrogen atom, and p represents an integer of 1 to 20.)

And a carboxyl group-containing photosensitive resin (A ′) obtained by reacting a reaction product with an unsaturated monocarboxylic acid (b) with a saturated and / or unsaturated polybasic acid anhydride (c).
Furthermore, as another aspect, there is provided a cured coating film obtained by curing the photocurable / thermosetting resin composition by irradiation with active energy rays and / or heating.

Hereinafter, each component of the photocurable thermosetting resin composition that can be developed with the alkaline aqueous solution of the present invention will be described in detail.
First, the carboxyl group-containing resin (A) containing one or more carboxyl groups in one molecule is a resin having a carboxyl group, specifically a carboxyl group having an ethylenically unsaturated double bond itself. Any of the containing photosensitive resin (A ′) and the carboxyl group-containing resin (A) having no ethylenically unsaturated double bond can be used, and is not limited to a specific one, Resins as listed (any of oligomers and polymers) can be suitably used.

(1) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) a carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(3) An unsaturated monocarboxylic acid is reacted with a copolymer of a compound having an epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride,
(4) A compound having a hydroxyl group and an unsaturated double bond in one molecule is reacted with a copolymer of an acid anhydride having an unsaturated double bond and another compound having an unsaturated double bond. The resulting carboxyl group-containing photosensitive resin,
(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) A hydroxyl group obtained by reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride and then reacting the resulting carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule; Carboxyl group-containing photosensitive resin,
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride, and (8) unsaturated to a polyfunctional oxetane compound having at least two oxetane rings in one molecule. Examples thereof include a carboxyl group-containing photosensitive resin obtained by reacting a monocarboxylic acid and reacting a saturated or unsaturated polybasic acid anhydride with a primary hydroxyl group in the resulting modified oxetane resin.
Among these, a carboxyl group-containing photosensitive resin having two or more photosensitive unsaturated double bonds in one molecule, particularly the carboxyl group-containing photosensitive resin (5) is preferable.

Furthermore, among the carboxyl group-containing photosensitive resins of (5) above, the following resins are suitable for use in semiconductor carrier tapes used for TAB, CSP, TCP, and flexible printed wiring boards such as COF. Further, it is possible to provide a cured product having excellent flexibility and less warping.
At least one polyfunctional epoxy compound (a) selected from the group consisting of compounds represented by the following general formula (II), the following general formula (III), and the following general formula (V)

（式中、Ｒ^３、Ｒ^４は、水素原子又はメチル基を表わし、Ｒ^５は、水素原子又はグリシジル基を表わし、ｎは、１〜５０の値を表わす。）

(In the formula, R ³ and R ⁴ represent a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a glycidyl group, and n represents a value of 1 to 50.)

（式中、Ｍは、下記一般式（IV）で示される基を表わし、Ｒ^６は、脂肪族又は芳香族多官能カルボン酸の残基を表わし、ｍは、１〜５０の値を表わす。）

(In the formula, M represents a group represented by the following general formula (IV), R ⁶ represents a residue of an aliphatic or aromatic polyfunctional carboxylic acid, and m represents a value of 1 to 50. )

（式中、Ｒ^７，Ｒ^８は、２価のシクロヘキサン環及び／又はベンゼン環を表わし、Ｒ^９，Ｒ^１０は、水素原子又はメチル基を表わし、Ｒ^１１は、水素原子又はグリシジル基を表わし、ｋは、０〜２５の値を表わす。）

(In the formula, R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, and R ¹¹ represents a hydrogen atom or a glycidyl group. , K represents a value from 0 to 25.)

（式中、ＸとＹは互いに異なる２価の芳香環を表わし、Ｇはグリシジル基及び／又は水素原子を表わし、ｐは、１〜２０の整数を表わす。）

と、不飽和モノカルボン酸（ｂ）との反応物に、飽和及び／又は不飽和多塩基酸無水物（ｃ）を反応させて得られるカルボキシル基含有感光性樹脂（Ａ’）である。

(In the formula, X and Y represent different divalent aromatic rings, G represents a glycidyl group and / or a hydrogen atom, and p represents an integer of 1 to 20.)

And a carboxyl group-containing photosensitive resin (A ′) obtained by reacting a reaction product with an unsaturated monocarboxylic acid (b) with a saturated and / or unsaturated polybasic acid anhydride (c).

Examples of the unsaturated monocarboxylic acid (b) include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and hydroxyethyl (meth) acrylate. , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, (meta ) Unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates, such as acrylic acid caprolactone adducts. Among the unsaturated monocarboxylic acids (b), acrylic acid and methacrylic acid are particularly preferable. These unsaturated monocarboxylic acids can be used alone or in combination of two or more.
Here, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  The addition amount of these unsaturated monocarboxylic acids (b) is 0.8 to 1.3 equivalents, preferably 0.95 to 1.0 per 1.0 equivalent of the epoxy group of the polyfunctional epoxy compound (a). 05 equivalents. When the addition amount of the unsaturated monocarboxylic acid (b) is less than 0.8 equivalent, the unreacted epoxy group is a carboxyl obtained from the saturated and / or unsaturated polybasic acid anhydride (c) to be added thereafter. This is not preferable because it reacts with a group to reduce storage stability or cause gelation. On the other hand, when the added amount exceeds 1.3 equivalents, the odor caused by the unsaturated monocarboxylic acid becomes strong, and excess unsaturated monocarboxylic acid gasifies during thermosetting, corroding copper foil and the like. This is not preferable.

  Examples of the saturated and / or unsaturated polybasic acid anhydride (c) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3, 6 -Alicyclic dibasic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl anhydride Aliphatic or aromatic dibasic acid or tribasic acid anhydride such as succinic acid, phthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic acid Dianhydride, cyclopentanetetracarboxylic Dianhydride, pyromellitic acid anhydride, an aliphatic or aromatic tetracarboxylic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride and the like, can be used one or two or more of these. Among these, alicyclic dibasic acid anhydrides are particularly preferable.

  The amount of the saturated and / or unsaturated polybasic acid anhydride (c) used is such that the resulting carboxyl group-containing photosensitive resin (A ′) has an acid value of 50 to 200 mgKOH / g, preferably 50 to 120 mgKOH / g. It is desirable that the added amount be in the range of. When the acid value of the carboxyl group-containing photosensitive resin (A ′) is less than 50 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.

Next, the polyfunctional epoxy compound (a) used as the raw material of these carboxyl group-containing photosensitive resin (A ') is demonstrated.
The epoxy compound represented by the general formula (II) is a bisphenol F type or bisphenol A type bifunctional epoxy compound in which all R ⁵ in the general formula (II) are hydrogen atoms and the value of n is 1 to 50. It is a polyfunctional bisphenol skeleton resin that is dissolved in an aprotic polar solvent such as dimethyl sulfoxide and reacted with an epihalohydrin and an alkali metal hydroxide as described below.
When the value of n in the general formula (II) is less than 1, it is not preferable because the dryness to the touch, the film forming property when forming a dry film and the crack resistance are deteriorated. On the other hand, when n exceeds 50, the developability is lowered and the resolution cannot be obtained, which is not preferable.

  Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromhydrin, β-methylepiiodohydrin, and the like. The addition amount of epihalohydrin is preferably 50% or more on average, more preferably 80% or more. When the added amount of epihalohydrin is less than 50%, it is difficult to obtain the development resistance when sensitized and the water resistance is lowered, which is not preferable.

  Further, as the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, and caustic soda is particularly preferable. The amount of the alkali metal hydroxide used is preferably 0.5 to 2 mol with respect to 1 mol of the alcoholic hydroxyl group to be epoxidized in the linear epoxy compound of the terminal epoxy group.

  The temperature of the epihalohydrin addition reaction is preferably 20 to 100 ° C. If the temperature of the addition reaction is less than 20 ° C., the reaction becomes slow and a long reaction is required. On the other hand, if the reaction temperature exceeds 100 ° C., many side reactions occur.

The epoxy compound represented by the general formula (III) will be described later using a bisphenol A type and / or bisphenol F type bifunctional epoxy compound and (d) a compound having at least two carboxyl groups in one molecule as raw materials. A linear epoxy compound having a terminal epoxy group obtained by alternately polymerizing using such a known esterification catalyst is converted into dimethyl, similarly to the polyfunctional epoxy compound (a) represented by the general formula (II). It is polyfunctionalized by dissolving in an aprotic polar solvent such as sulfoxide and reacting epihalohydrin with an alkali metal hydroxide.
When the value of m in the general formula (III) is less than 1, it is not preferable because the dryness to the touch, the film forming property and the crack resistance when forming a dry film are lowered. On the other hand, when m exceeds 50, the developability is deteriorated and the resolution cannot be obtained. Moreover, the addition amount of epihalohydrin is preferably 50% or more on average, and more preferably 80% or more. When the added amount of epihalohydrin is less than 50%, it is difficult to obtain the development resistance when sensitized and the water resistance is lowered, which is not preferable.

  Examples of the compound (d) having at least two carboxyl groups in one molecule include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and phthalic acid. , Isophthalic acid, terephthalic acid, succinic acid, adipic acid, muconic acid, suberic acid, sebacic acid, an adduct of 2-hydroxy-2-methylsuccinic acid and phthalic anhydride, etc. 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, adipic acid, muconic acid, suberic acid, sebacic acid and other aliphatic or cycloaliphatic The dicarboxylic acid compound is particularly preferred. These can be used alone or in combination of two or more.

Examples of the esterification catalyst include phosphines, alkali metal compounds, amines and the like that can quantitatively react an epoxy group and a carboxyl group. Specifically, phosphines such as trialkylphosphine and triarylphosphine such as tributylphosphine and triphenylphosphine or salts thereof with oxides; hydroxides of alkali metals such as sodium, lithium and potassium, halides, alcoholates, Amides, etc .; aliphatic or aromatic primary, secondary, primary such as triethanolamine, N, N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide A tertiary, a quaternary amine, etc. are mentioned, These can be used individually or in combination of 2 or more types.
The amount of these catalysts used is desirably 0.1 to 25 mol% with respect to 1 mol (1 equivalent) of the epoxy group of the bisphenol A type and / or bisphenol F type bifunctional epoxy compound. Preferably it is a ratio of 0.5-20 mol%, More preferably, it is a ratio of 1-15 mol%. The reason for this is that when the amount of the catalyst used is less than 0.1 mol%, the reaction takes time and is not economical. On the other hand, when it exceeds 25 mol%, the reaction is fast and difficult to control. Therefore, it is not preferable.

  The epoxy compound represented by the general formula (V) includes an aromatic epoxy compound having two glycidyl groups in one molecule (hereinafter referred to as a bifunctional aromatic epoxy compound) and two phenolic compounds in one molecule. Using a bifunctional phenol compound having a hydroxyl group as a raw material, using a known etherification catalyst as described later, a linear epoxy compound having a terminal epoxy group obtained by alternately polymerizing in a solvent or in the absence of a solvent, Similar to the polyfunctional epoxy compound (a) represented by the general formula (II), it was dissolved in an aprotic polar solvent such as dimethyl sulfoxide and reacted with an epihalohydrin and an alkali metal hydroxide. Is.

  Examples of the bifunctional aromatic epoxy compound that is a raw material of the general formula (V) include biphenol diglycidyl ether, bixylenol diglycidyl ether having an aromatic ring represented by the following formulas (VI) to (IX), At least one bifunctional aromatic epoxy compound such as bisphenol type diglycidyl ether or naphthalene type diglycidyl ether is used. By using such a bifunctional aromatic epoxy compound as one monomer component in an alternating copolymer with a bifunctional aromatic alcohol, an epoxy compound excellent in strength, heat resistance, electrical insulation and the like of the cured product can be obtained. can get.

（式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５は同一の又は互いに異なる、水素原子又は炭素数１〜４のアルキル基を表わし、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９は同一の又は互いに異なる、水素原子、炭素数１〜４のアルキル基又はハロゲン原子を表わし、Ｒ^２０、Ｒ^２１は同一の又は互いに異なる、水素原子、メチル基又はハロゲン化メチル基を表わす。）

(In the formula, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are the same. Or a different hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ²⁰ and R ²¹ represent the same or different hydrogen atom, methyl group or halogenated methyl group.

  As the biphenol type, bixylenol type, bisphenol type or naphthalene type diglycidyl ether, for example, a biphenol compound, a bixylenol compound, a bisphenol compound, or one produced from a reaction of dihydroxynaphthalene and epichlorohydrin can be used. Commercially available epoxy compounds can also be used. For example, as biphenol type diglycidyl ether, trade name “Epicoat YL-6056” manufactured by Yuka Shell Epoxy Co., Ltd., and as bixylenol type diglycidyl ether, oil can be used. Bisphenol A type such as “Araldite # 260” and “Araldite # 6071” manufactured by Asahi Chiba Co., Ltd. as bisphenol-type diglycidyl ether, such as “Epicoat YX-4000” manufactured by Kasei Shell Epoxy Co., Ltd. Epoxy compounds or bisphenol F type epoxy compounds such as “Epicron 830S” trade name manufactured by Dainippon Ink and Chemicals, Inc. or bisphenol S types such as “Epicron EXA1514” manufactured by Dainippon Ink and Chemicals, Inc. Epoxy compound, naphthalene type diglycidyl ester The ether can be exemplified by Dainippon Ink & trade name "Epiclon HP-4032 (D)" or the like, may be used singly or in combinations of two or more.

  The bifunctional phenol compound as a raw material of the general formula (V) is characterized by its structure, has an aromatic ring to increase heat resistance, and has a symmetrical structure or a rigid structure. be able to. Examples of such compounds include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene and the like. Dihydroxynaphthalene derivatives, biphenol derivatives such as bixylenol and biphenol, bisphenol derivatives such as bisphenol A, bisphenol F, bisphenol S and alkyl group-substituted bisphenol, hydroquinone derivatives such as hydroquinone, methylhydroquinone and trimethylhydroquinone, etc. These can be used alone or in combination of two or more.

  The etherification catalyst used for the reaction between the bifunctional aromatic epoxy compound and the bifunctional phenol compound is a phosphine, an alkali metal compound or an amine that can react quantitatively with a glycidyl group and a phenolic hydroxyl group. Or in combination. Other catalysts are not preferable because they react with an alcoholic hydroxyl group produced by the reaction between a glycidyl group and a phenolic hydroxyl group to form a gel. Examples of phosphines include trialkyl phosphines such as tributyl phosphine and triphenyl phosphine, and salts of these with oxides. Examples of the alkali metal compound include hydroxides, halides, alcoholates, amides, and the like of alkali metals such as sodium, lithium and potassium, and these can be used alone or in combination of two or more. Examples of the amines include aliphatic or aromatic primary, secondary, tertiary, and quaternary amines, and these can be used alone or in combination of two or more. Specific examples of amines include triethanolamine, N, N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like.

  These etherification catalysts are used in the range of 0.001 to 1 part by mass, preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the charged amount of the bifunctional aromatic epoxy compound and the bifunctional phenol compound. Is preferred. The reason for this is that if the amount of the catalyst used is less than 0.001 part by mass, the reaction takes time and is not economical. On the other hand, if it exceeds 1 part by mass, the reaction is fast and difficult to control. Absent. In the presence of such a catalyst, the reaction between the bifunctional aromatic epoxy resin compound and the bifunctional phenol compound is carried out in an inert gas stream or in the air in the temperature range of about 130 to 180 ° C. under the catalyst. Is preferred.

  Examples of the compound (B) having two or more ethylenically unsaturated bonds in one molecule used in the photocurable / thermosetting resin composition of the present invention include 2-hydroxyethyl acrylate, 2-hydroxy Hydroxyl-containing acrylates such as propyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate; water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di Polyfunctional polyester acrylates of polyfunctional alcohols such as pentaerythritol hexaacrylate; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A Ethylene oxide adducts of polyfunctional phenols such as bisphenol A and biphenol, acrylates of propylene oxide adducts; polyfunctional or monofunctional polyurethane acrylates that are isocyanate modified products of the above hydroxyl group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol Acrylic acid adduct of A diglycidyl ether or phenol novolac epoxy resin, and methacrylates corresponding to the above acrylates can be mentioned, and these can be used alone or in combination of two or more. . Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups in one molecule is preferable.

Examples of the photopolymerization initiator (C) used in the photocurable / thermosetting resin composition of the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] Aminoacetophenones such as 2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone 2-ethylanthraquino Anthraquinones such as 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal And ketones such as benzyldimethyl ketal; benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone or xanthones; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added.
In addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction.
Among these, particularly preferred photopolymerization initiators are 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one and the like, but not limited to these, those that absorb light in the ultraviolet or visible light region and radically polymerize unsaturated groups such as (meth) acryloyl groups As long as it is not limited to the photopolymerization initiator and the photoinitiator aid, they can be used alone or in combination.

  The amount of the photopolymerization initiator (C) used (the total amount when photoinitiators are used) is the same as the carboxyl group-containing resin (A) and / or the carboxyl group-containing photosensitive resin (A ′). The total of the compound (B) having two or more ethylenically unsaturated bonds in one molecule is 0.1 to 25 parts by mass, preferably 0. A ratio of 5 to 20 parts by mass is desirable. When the blending amount of the photopolymerization initiator (C) is less than the above range, it is not cured even when active energy rays are irradiated, or it is necessary to increase the irradiation time, and it is difficult to obtain appropriate coating properties. . On the other hand, even if the photopolymerization initiator (C) is added in a larger amount than the above range, there is no change in photocurability, which is not economically preferable.

The phosphoric acid amide (D) represented by the following general formula (I), which is a feature of the non-halogen flame-retardant photocurable and thermosetting resin composition of the present invention,

（式中、Ｒ^１，Ｒ^２は、同一又は異なるもので、水素原子又は炭素数１〜４のアルキル基を表わす。）

ジフェニルホスフィニルクロリド、ジフェニルホスフィニルブロミド、ジ−３，５−キシレニルホスフィニルクロリドなどの水素原子又は炭素数１〜４のアルキル基が付いたジアリールホスフィニルハライド類、好ましくはジフェニルホスフィニルクロリドと、ピペラジンをジクロロエタンなどの非水系有機溶剤に溶解し、トリエチルアミンなどの塩基触媒を加えることにより、合成することができる。例えば、ジフェニルホスフィニルクロライドとピペラジンから、誘導される上記一般式（Ｉ）のＲ^１及びＲ^２が、水素原子であるＮ，Ｎ’−ビス（ジフェノキシフォスフィニル）ピペラジンは、リン原子を約１１質量％、窒素原子を約５質量％含んでおり、融点は、約１８６．７℃である。市販品としては、四国化成社製のＳＰ−７０３がある。
この様にして得られた上記一般式（Ｉ）で表わされるリン酸アミド化合物（Ｄ）は、リン酸エステル類に比べ、加水分解性が極めて低く、又融点も高いという特徴を有している。更に、分子中に窒素原子を含んでいることから、燃焼時にホスファゼン等を形成し、リン酸エステルに比べ、難燃性付与効果も高いという特徴を有している。
上記一般式（Ｉ）で表わされるリン酸アミドの配合量としては、本発明の光硬化性・熱硬化性樹脂組成物中に５〜５０質量％、好ましくは１０〜４０質量％、より好ましくは２０〜４０質量％である。リン酸アミドの配合量が、５質量％未満の場合、リン原子の含有率が低く、他の難燃剤と併用しても、充分な難燃性が得られないので好ましくない。一方、リン酸アミドの配合量が５０質量％を超えた場合、塗膜強度が低下するので好ましくない。

(In formula, R < ¹ >, R < ² > is the same or different, and represents a hydrogen atom or a C1-C4 alkyl group.)

Diarylphosphinyl halides with a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as diphenylphosphinyl chloride, diphenylphosphinyl bromide, di-3,5-xylenylphosphinyl chloride, preferably It can be synthesized by dissolving diphenylphosphinyl chloride and piperazine in a non-aqueous organic solvent such as dichloroethane and adding a base catalyst such as triethylamine. For example, N, N′-bis (diphenoxyphosphinyl) piperazine in which R ¹ and R ² of the above general formula (I) derived from diphenylphosphinyl chloride and piperazine are hydrogen atoms is a phosphorus atom About 11% by mass, about 5% by mass of nitrogen atoms, and the melting point is about 186.7 ° C. As a commercial item, there is SP-703 manufactured by Shikoku Kasei Co., Ltd.
The phosphoric acid amide compound (D) represented by the above general formula (I) thus obtained is characterized by extremely low hydrolyzability and high melting point as compared with phosphoric acid esters. . Furthermore, since the molecule contains a nitrogen atom, phosphazene and the like are formed during combustion, and the flame retardancy-imparting effect is higher than that of phosphate esters.
As a compounding quantity of the phosphoric acid amide represented by the said general formula (I), 5-50 mass% in the photocurable thermosetting resin composition of this invention, Preferably it is 10-40 mass%, More preferably 20 to 40% by mass. When the amount of phosphoric acid amide is less than 5% by mass, the phosphorus atom content is low, and even when used in combination with other flame retardants, sufficient flame retardancy cannot be obtained, such being undesirable. On the other hand, when the blending amount of phosphoric acid amide exceeds 50% by mass, the coating film strength decreases, which is not preferable.

  As the compound (E) having one or more oxirane rings and / or oxetane rings in one molecule of the present invention, a polyfunctional epoxy compound (E-1) having two or more oxirane rings in one molecule, Examples thereof include a polyfunctional oxetane compound (E-2) having two or more oxetane rings in one molecule and a compound (E-3) having one or more oxirane rings and oxetane rings in one molecule.

  Examples of the polyfunctional epoxy compound (E-1) include novolak-type epoxy resins (for example, novolak resins obtained by reacting phenols such as phenol, cresol, halogenated phenol, and alkylphenol with formaldehyde in the presence of an acid catalyst. , Obtained by reacting epichlorohydrin and / or methyl epichlorohydrin, and commercially available products include EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN manufactured by Nippon Kayaku Co., Ltd. -S; DEN-431, DEN-438 manufactured by Dow Chemical Company; N-730, N-770, N-865, N-665, N-673, N-695 manufactured by Dainippon Ink & Chemicals, Inc. , VH-4150, etc.), bisphenol A type epoxy resin ( For example, it is obtained by reacting bisphenols such as bisphenol A and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, and commercially available products include Epicoat 1004 and Epicoat 1002 manufactured by Yuka Shell Epoxy Co., Ltd .; DER-330 manufactured by Dow Chemical Co., DER-337, etc.), trisphenol methane type epoxy resin (for example, trisphenol methane, triskresol methane, etc., and epichlorohydrin and / or methyl epichlorohydrin are obtained, Commercially available products include EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd.), tris (2,3-epoxypropyl) isocyanurate, biphenol diglycidyl ether, and other alicyclic epoxies. Resins, amino group-containing epoxy resin, copolymerized epoxy resins, cardo type epoxy resin, a conventionally known epoxy resins such as calixarene type epoxy resins may be used alone or in combinations of two or more.

The polyfunctional oxetane compound (E-2) used in the present invention can be obtained, for example, by etherification or esterification using oxetane alcohols such as 3-ethyl-3-hydroxymethyloxetane as a raw material. Specifically, 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene, 3-ethyl-3-hydroxymethyloxetane (trade name OXT-101 manufactured by Toagosei Co., Ltd.), 3 -Ethyl-3- (phenoxymethyl) oxetane (trade name OXT-211 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name OXT-212 manufactured by Toagosei Co., Ltd.) 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (trade name OXT-121 manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether (Toagosei) The product name OXT-221) manufactured by the company is mentioned. Furthermore, phenol novolac type oxetane compounds and the like can also be mentioned.
These polyfunctional oxetane compounds (E-2) can be used alone or in combination of two or more.

  Examples of the compound (E-3) having at least one oxirane ring and oxetane ring in each molecule used in the present invention include oxetane alcohols such as 3-ethyl-3-hydroxymethyloxetane and glycidol. Examples include etherified compounds, and compounds obtained by adding polycarboxylic acid together with these compounds and esterifying them.

  The compounding amount of the compound (E) having one or more oxirane rings and / or oxetane rings in one molecule is 0.6 to 2 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). 0.0 equivalent is preferable from the viewpoint of characteristics such as plating resistance and solder heat resistance of the cured coating film. When the said compounding quantity is less than 0.6 equivalent, since the alkali resistance and plating resistance of hardened | cured material fall, it is unpreferable. On the other hand, when the amount exceeds 2.0 equivalents, the compound (E) having one or more oxirane rings and / or oxetane rings in the molecule remaining as an unreacted substance is not preferable because the heat resistance and the like are lowered.

In the photocurable / thermosetting resin composition of the present invention, a diluent solvent may be added to adjust the viscosity of the composition.
Examples of the diluting solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, and acetic acid ester of the above glycol ethers; ethanol, propanol, ethylene glycol, propylene glycol Alcohols such as octane, decane, etc .; petroleum ether, petroleum naphtha, hydrogenated naphtha, solvent naphtha, etc. Organic solvents, such as oil-based solvents. You may use these individually or in combination of 2 or more types.
Although the compounding quantity of these diluents is not specifically limited, It is 300 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin. The ratio is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, from the viewpoint of coating properties and ensuring the film thickness of the dried coating film.

  If necessary, the photocurable / thermosetting resin composition of the present invention may further include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, spherical Known or commonly used inorganic fillers such as silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica can be used alone or in combination. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The blending amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A).

Furthermore, the photocurable / thermosetting resin composition of the present invention can be colored with an inorganic pigment, an organic pigment, an organic dye, etc., but the organic dye causes a decrease in sensitivity. Or it is preferable to use an organic pigment. Specific examples include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black. Furthermore, it is particularly preferable to use a halogen-free organic pigment from the viewpoint of environmental problems.
In addition, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc .; known conventional thickening agents such as finely divided silica, organic bentonite, montmorillonite, etc. Agents: silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents; imidazole-based, thiazole-based, triazole-based, adhesion-imparting agents such as silane coupling agents, etc. Can be blended.
In order to further increase the flame retardancy, a phosphorus-containing compound having a low hydrolyzability such as a phosphazene compound can be blended.

The photocurable / thermosetting composition of the present invention is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. By evaporating and drying (temporarily drying) the organic solvent contained in the composition at a temperature, it is possible to form a coating film having excellent touch drying properties and a long development life. Then, it can be selectively exposed with actinic rays through a photomask on which a pattern has been formed, and a resist pattern can be formed by developing an unexposed portion with a dilute aqueous alkali solution. As a result, an insulating coating film excellent in adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation and corrosion resistance is formed.

As the dilute alkaline aqueous solution, dilute alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as an actinic ray for exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, “parts” and “%” are based on mass unless otherwise specified.

<Synthesis Example 1> Synthesis of carboxyl group-containing photosensitive resin (A ') A cresol novolac epoxy resin (Epicron N-680, Dainippon Ink, Inc.) was placed in a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser. 210 parts by chemical industry, epoxy equivalent = 210) and 109.7 parts of carbitol acetate were weighed and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., 76.1 parts of tetrahydrophthalic anhydride was added, and about 6 hours until the absorption peak of acid anhydride (1780 cm ⁻¹ ) disappeared by infrared absorption analysis. Reacted. To this reaction solution, 109.7 parts of the aromatic solvent ipsol # 150 manufactured by Idemitsu Petrochemical Co., Ltd. was added, diluted, and taken out. The carboxyl group-containing photosensitive resin (A ′) varnish thus obtained had a nonvolatile content of 62% and a solid acid value of 78 mgKOH / g. Hereinafter, this reaction solution is referred to as A-1 varnish.

<Synthesis Example 2> Synthesis of carboxyl group-containing photosensitive resin (A ') In a flask equipped with a stirrer, a condenser tube and a thermometer, a bisphenol F type epoxy resin (epoxy equivalent = 950, softening point 85 ° C, average polymerization degree) n = 6.2) 380 parts and epichlorohydrin 925 parts were charged and dissolved in 462.5 parts of dimethyl sulfoxide, and then 60.9 parts (1.5 mol) of 98.5% pure sodium hydroxide at 70 ° C. with stirring. Was added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, 250 parts of water was added and washed with water. After the oil / water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered from the oil layer by distillation under reduced pressure, and the reaction product containing the remaining replication salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% water. 10 parts of an aqueous sodium oxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After oil-water separation, til isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 and a softening point of 69 ° C. When the obtained polyfunctional epoxy compound (a) represented by the general formula (II) is calculated from the epoxy equivalent, about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin are epoxy. It was made. 310 parts of this polyfunctional epoxy compound (a) and 313.2 parts of carbitol acetate were charged into a four-necked flask equipped with a stirrer and a reflux condenser, and heated and stirred at 90 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 60 hours, and the acid value is 0.2 mg KOH. / G of reaction product was obtained. To this, 140 parts of tetrahydrophthalic anhydride is added, heated to 90 ° C. and reacted until the solid content acid value reaches 100 mgKOH / g, and contains 62.5% of carboxyl group-containing photosensitive resin (A ′). A solution was obtained. Hereinafter, this solution is referred to as A-2 varnish.
<Examples 1 and 2 and Comparative Examples 1 and 2>

The compounding components shown in Table 1 using each varnish obtained in the synthesis example were premixed and then kneaded with a three-roll mill to obtain a photocurable / thermosetting resin composition. Table 2 shows the evaluation results of each photocurable and thermosetting resin composition.

なお、上記表２中の性能試験の方法は、以下の通りである。

性能評価：

The performance test method in Table 2 is as follows.

Performance evaluation:

(1) Flame retardancy The above-mentioned photocurable / thermosetting resin composition is applied to a non-halogen flame retardant substrate RO-67G (0.2 mmt material) manufactured by Hitachi Chemical Co., Ltd. After applying the entire surface by screen printing and drying at 80 ° C. for 15 minutes, the entire surface is similarly applied to the back surface, followed by drying at 80 ° C. for 20 minutes, and both surfaces are exposed under the condition of an exposure amount of 300 mJ / cm ² . Development was performed at 30 ° C. and 1% Na ₂ CO ₃ aqueous solution for 60 seconds under the condition of a spray pressure of 0.2 MPa. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate.
The test piece was measured for burning time according to the UL94 flammability test.
○: UL V-0 equivalent
(The total combustion time when 5 test pieces are ignited twice each is 50 seconds or less)
(Triangle | delta): UL V-1 equivalent (The total combustion time when each of five test pieces is ignited twice is 50 to 250 seconds)
X: No self-extinguishing (total burning time when igniting 5 test pieces twice each is 250 seconds or more)

(2) Solder heat resistance The above-mentioned photocurable / thermosetting resin composition is applied to the printed circuit board on which the circuit is formed by screen printing so that the dry coating film has a thickness of about 20 μm. After partial drying, pattern exposure was performed under an exposure amount of 300 mJ / cm ² , and development was performed at 30 ° C. and a 1% Na ₂ CO ₃ aqueous solution for 60 seconds under a spray pressure of 0.2 MPa. A rosin-based flux was applied to the obtained cured coating film and immersed in a solder bath at 260 ° C. for 10 seconds, and the state of the cured coating film was evaluated according to the following criteria.
○: The cured coating has no blistering, peeling or discoloration
Δ: Slightly blistered, peeled, or discolored on the cured coating film
X: The cured coating has blistering, peeling, or discoloration

(3) Acid resistance The substrate obtained in the same manner as above was immersed in a 10 vol% sulfuric acid aqueous solution at 50 ° C. for 30 minutes, washed with water, and then subjected to a peel test using a cellophane adhesive tape to evaluate the peeling and discoloration of the resist. did.
○: No change at all △: Slightly changed ×: The film has peeling

(4) Alkali resistance In the same manner as the above acid resistance, the obtained substrate was immersed in a 10 wt% sodium hydroxide solution at 50 ° C. for 30 minutes, washed with water, and then subjected to a peel test using a cellophane adhesive tape. The peeling / discoloration was evaluated.
○: No change at all △: Slightly changed ×: The film has peeling

As is apparent from the results shown in Table 2, the cured coating film obtained from the photocurable / thermosetting resin composition of the present invention is non-halogen, flame retardant, and has chemical resistance such as acid resistance and alkali resistance. It has excellent properties. On the other hand, in Comparative Example 1 in which the phosphoric acid amide compound represented by the general formula (I) is not blended, flame retardancy cannot be obtained, while the phosphoric acid tribasic phosphoric acid flame retardant is triphosphate. Although the comparative example 2 which mix | blended phenyl showed the flame retardance, acid resistance and alkali resistance were inferior.

Claims (5)

(A) a carboxyl group-containing resin containing one or more carboxyl groups in one molecule;
(B) a compound having two or more ethylenically unsaturated bonds in one molecule;
(C) a photopolymerization initiator,
(D) a phosphoric acid amide compound represented by the following general formula (I):

(In formula, R < ¹ >, R < ² > is the same or different, and represents a hydrogen atom or a C1-C4 alkyl group.)

And (E) a photocurable / thermosetting resin composition developable with an aqueous alkali solution, comprising a compound having one or more oxirane rings and / or oxetane rings in one molecule. 2. The light according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing photosensitive resin further having (A ′) two or more ethylenically unsaturated bonds in one molecule. Curable and thermosetting resin composition. The carboxyl group-containing photosensitive resin (A ′) is at least one polyfunctional selected from the group consisting of compounds represented by the following general formula (II), the following general formula (III), and the following general formula (V). Epoxy compound (a)

(In the formula, R ³ and R ⁴ represent a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a glycidyl group, and n represents a value of 1 to 50.)

(In the formula, M represents a group represented by the following general formula (IV), R ⁶ represents a residue of an aliphatic or aromatic polyfunctional carboxylic acid, and m represents a value of 1 to 50. )

(In the formula, R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, and R ¹¹ represents a hydrogen atom or a glycidyl group. , K represents a value from 0 to 25.)

(In the formula, X and Y represent different divalent aromatic rings, G represents a glycidyl group and / or a hydrogen atom, and p represents an integer of 1 to 20.)

And a product obtained by reacting a reaction product of the unsaturated monocarboxylic acid (b) with a saturated and / or unsaturated polybasic acid anhydride (c). Photo-curable / thermosetting resin composition. The photocurable / thermosetting resin composition according to any one of claims 1 to 3, wherein the phosphoric acid amide compound (D) is contained in the composition in an amount of 5 to 50 mass%. A cured coating film obtained by curing the photocurable / thermosetting resin composition according to any one of claims 1 to 4 by irradiation with active energy rays and / or heating.