JP2005232195A - Thermosetting resin composition and its cured coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which reduces hydrolyzing properties useful as a solder resist used in manufacturing printed-wiring boards and a marking ink, excels in heat resistance, chemical resistance, adhesion, electrical insulation properties and the like, is halogen-free, and has stabilized flame retardance, furthermore a thermosetting resin composition which excels in folding resistance suitably used in a semiconductor carrier tape and a solder resist for flexible printed-wiring boards and reduces warpage after curing, and its cured coating film. <P>SOLUTION: The thermosetting resin composition comprises (A) a carboxyl group-containing unsaturated polyester resin having one or more carboxyl groups and an ethylenically unsaturated group in one molecule, (B) a resin having two or more epoxy groups in one molecule, (C) an amine based active hydrogen compound, and (D) a phosphoric acid amide compound represented by formula (I). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a halogen-free and flame-retardant thermosetting resin composition useful for the production of printed wiring boards. More specifically, it has low hydrolyzability useful as a solder resist and marking ink for printed wiring boards, has excellent solder heat resistance, chemical resistance, adhesion, electrical insulation, etc., and is halogen-free and stable flame retardant. Thermosetting resin composition, flexible printed wiring boards such as semiconductor carrier tape and COF (Chip on Film) used for TAB (Tape Automated Bonding), CSP (Chip Size Package), and TCP (Tape Carrier Package) The present invention relates to a thermosetting resin composition that is excellent in folding resistance and is less warped after curing, and a cured coating film thereof.

Solder resist used in the production of printed wiring boards not only protects irrelevant wiring during the soldering process, but may also be used as plating resist during plating processing. Therefore, heat resistance during soldering, chemical resistance during plating, insulation reliability after soldering, etc. are required. In addition, the solder resist of flexible printed wiring boards such as semiconductor carrier tape and COF (Chip on Film) used in TAB (Tape Automated Bonding), CSP (Chip Size Package), and TCP (Tape Carrier Package) is further resistant to resistance. It is required to be a cured coating film that has excellent foldability and little warpage after curing.
Further, printed wiring boards and the like used for devices other than battery-driven devices are also required to be flame retardant. Furthermore, as a method of making such flame retardant, since halogen compounds contained in resins and organic materials may cause dioxins in the incinerated ash, flame resistance imparting by halogen-free is recently provided. It is requested.

Examples of such a solder resist and marking ink include a composition comprising a liquid epoxy resin, an extender pigment, a color pigment, a solvent, and an imidazole derivative (see Patent Document 1), acrylic acid or methacrylic acid and styrene, etc. A composition comprising a copolymer and an epoxy resin (see Patent Document 2) has been proposed, but the plating resistance and the like were insufficient. Moreover, when these were used for a semiconductor carrier tape or a flexible printed wiring board, there existed a problem that bending resistance was inadequate and the curvature after hardening was also large.
Furthermore, as a general method for flame retarding such a thermosetting resin composition, a method of blending a halogen compound such as a brominated epoxy resin, a method of blending a phosphate ester as a flame retardant, and red phosphorus And the like. However, at the present time that halogen-free products are being sought, methods of blending halogen compounds such as brominated epoxy resins are avoided. In addition, the method of blending phosphoric acid ester has a problem that the phosphoric acid ester is hydrolyzed by plating treatment at the time of manufacturing a printed wiring board, and the coating properties such as electric insulation and electric corrosiveness are lowered. Further, the method of blending red phosphorus has problems such as poor appearance such as coloring with red phosphorus, and regulations such as the Fire Service Act when the solder resist composition is stored.

As a solder resist for flexible printed wiring boards, a type of film that has a flexible film, or a type that is bonded using an adhesive after punching a polyimide film called a coverlay film with a mold that matches the pattern, is used. There are a type in which a curable or thermosetting type solder resist ink or liquid polyimide ink is applied by screen printing, and a liquid photo solder resist ink type in which a flexible film is formed.
However, the cover lay film can be made flame-retardant by halogen-free, but has a problem in that it cannot form a highly accurate pattern because it has a problem of following with the copper foil. On the other hand, the ultraviolet curable solder resist ink and the liquid photo solder resist ink have a problem that the adhesiveness with the polyimide of the base material is poor and sufficient flexibility cannot be obtained. Further, since the curing shrinkage of the solder resist ink and the cooling shrinkage after curing are large, warping occurs, which is a problem. Furthermore, a composition using a soluble aromatic polyimide as a liquid polyimide ink has been proposed (see Patent Document 3), but it is expensive and bleeding occurs during printing, so that sufficient workability cannot be obtained. It is a problem.
JP-A-50-6408 (Claims) JP-A-4-239070 (Claims) Japanese Patent Publication No. 5-75032 (Claims)

The present invention has been made in order to solve the above-mentioned problems of the prior art, and its main purpose is low hydrolyzability useful as solder resist and marking ink used in printed wiring board production, and solder heat resistance. Suitable for thermosetting resin composition with excellent flame resistance, chemical resistance, adhesion, electrical insulation, etc., halogen-free and stable flame retardancy, and solder resist for semiconductor carrier tape and flexible printed wiring board An object of the present invention is to provide a thermosetting resin composition having excellent folding resistance and less warping after curing.
Another object of the present invention is that the above thermosetting resin composition is low in hydrolyzability obtained by curing by heating, excellent in solder heat resistance, chemical resistance, adhesion, electrical insulation, etc. Another object of the present invention is to provide a cured coating film which 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 unsaturated polyester resin having one or more carboxyl groups and ethylenically unsaturated groups in one molecule,
(B) a resin having two or more epoxy groups in one molecule;
(C) an amine-based active hydrogen compound,
And (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のアルキル基を示す。）

を含有する熱硬化性樹脂組成物が、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、かつ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、さらに、上記カルボキシル基含有不飽和ポリエステル樹脂（Ａ）として、特定の線状の多官能エポキシ化合物（ａ）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樹脂を用いた組成物が、耐折性に優れ、硬化後の反りが少ない硬化塗膜が得られることを見出し、本発明を完成するに至った。

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

Has been found that the thermosetting resin composition containing is low in hydrolyzability, excellent in solder heat resistance, chemical resistance, adhesion, electrical insulation, etc., and has halogen-free and stable flame retardancy, Furthermore, as the carboxyl group-containing unsaturated polyester resin (A), a reaction product of a specific linear polyfunctional epoxy compound (a) and an unsaturated monocarboxylic acid (b) may be saturated and / or unsaturated polyvalent. It has been found that a composition using a resin obtained by reacting a basic acid anhydride (c) can provide a cured coating film that has excellent folding resistance and little warpage after curing, and has completed the present invention. It was.

  That is, the present inventors carried out an addition reaction between a carboxyl group of a carboxyl group-containing unsaturated polyester resin (A) and an epoxy group of a resin (B) having two or more epoxy groups in one molecule, and a carboxyl group. By taking a crosslinked form using the Michael addition reaction of the ethylenically unsaturated group of the contained unsaturated polyester resin (A) and the active hydrogen of the amine-based active hydrogen compound (C), the hydrolyzability is low, the solder heat resistance, It becomes a resin composition excellent in chemical resistance, adhesion, electrical insulation, etc., and further, by blending the phosphoric acid amide compound (D) represented by the above general formula (I), the hydrolyzability is low, and halogen It has been found that free and stable flame retardancy can be imparted. Furthermore, as the carboxyl group-containing unsaturated polyester resin (A), a reaction product of a linear polyfunctional epoxy compound (a) and an unsaturated monocarboxylic acid (b) described later may be saturated and / or unsaturated polyvalent. It has been found that by using a resin obtained by reacting the basic acid anhydride (c), a cured coating film having excellent folding resistance and less warping after curing can be obtained, and the present invention has been completed.

  By using the thermosetting resin composition of the present invention, it has halogen-free and stable flame retardancy that does not generate environmentally destructive substances such as dioxins, has low hydrolyzability, solder heat resistance, A solder resist for printed wiring boards and marking ink that are excellent in chemical properties, adhesion, electrical insulation, etc. are provided, and a highly reliable printed wiring board can be manufactured at low cost. Furthermore, by using a specific carboxyl group-containing unsaturated polyester resin (A), it is excellent in folding resistance suitably used for a semiconductor carrier tape used for TAB, CSP, TCP, and a flexible printed wiring board such as COF, A highly reliable flexible printed wiring board having a cured coating film with less warping can be provided at low cost.

As a first aspect of the present invention, (A) a carboxyl group-containing unsaturated polyester resin having one or more carboxyl groups and ethylenically unsaturated groups in one molecule,
(B) a resin having two or more epoxy groups in one molecule;
(C) an amine-based active hydrogen compound,
And (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のアルキル基を示す。）

を含有することを特徴とする熱硬化性樹脂組成物が提供される。また、本発明の好ましい態様として、前記カルボキシル基含有不飽和ポリエステル樹脂（Ａ）が、下記一般式（II）、下記一般式（III）、及び下記一般式（Ｖ）で表わされるエポキシ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 shows a hydrogen atom or a C1-C4 alkyl group.)

The thermosetting resin composition characterized by containing is provided. As a preferred embodiment of the present invention, the carboxyl group-containing unsaturated polyester resin (A) is composed of an epoxy compound represented by the following general formula (II), the following general formula (III), and the following general formula (V). At least one polyfunctional epoxy compound (a) selected from the group

（式中、Ｒ^３，Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は水素原子又はグリシジル基を示し、ｎは１〜５０の値を示す。）

^(Wherein, R 3, ^{R 4} represents a hydrogen atom or a methyl group, ^{R 5} represents a hydrogen atom or a glycidyl radical, n denotes a value of 1-50.)

（式中、Ｍは下記一般式（IV）で表わされる基を示し、Ｒ^６は脂肪族又は芳香族多官能カルボン酸の残基を示し、ｍは１〜５０の値を示す。）

(In the formula, M represents a group represented by the following general formula (IV), R ⁶ represents an aliphatic or aromatic polyfunctional carboxylic acid residue, 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／又はベンゼン環を示し、Ｒ^９，Ｒ^１０は水素原子又はメチル基を示し、Ｒ^１１は水素原子又はグリシジル基を示し、ｋは０〜２５の値を示す。）

(Wherein R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or a benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, R ¹¹ represents a hydrogen atom or a glycidyl group, and k represents Shows values from 0 to 25.)

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

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樹脂であることを特徴とする熱硬化性樹脂組成物が提供される。
さらに、他の態様としては、上記熱硬化性樹脂組成物を、加熱により硬化させて得られ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 resin obtained by reacting a reaction product of the unsaturated monocarboxylic acid (b) with a saturated and / or unsaturated polybasic acid anhydride (c). Is provided.
Furthermore, as another aspect, a cured coating film obtained by curing the thermosetting resin composition by heating is provided.

Hereinafter, each component of the thermosetting resin composition of the present invention will be described in detail.
First, as the carboxyl group-containing unsaturated polyester resin (A) having at least one carboxyl group and ethylenically unsaturated group in one molecule used in the present invention, a carboxyl group and an ethylenically unsaturated group are contained in the molecule. If it has, it will not be limited to a specific thing, but especially resin (any of an oligomer and a polymer) as enumerated below can be used conveniently.

(1) A carboxyl group-containing unsaturated polyester resin obtained by using an ethylenically unsaturated group as a pendant using glycidyl methacrylate or acrylic acid chloride as a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) 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 unsaturated polyester resin obtained by reacting a saturated or unsaturated polybasic acid anhydride,
(3) A compound having an unsaturated double bond and a copolymer having a compound having an unsaturated double bond are reacted with a compound having a hydroxyl group and an unsaturated double bond in one molecule. Carboxyl group-containing unsaturated polyester resin obtained,
(4) a carboxyl group-containing unsaturated polyester 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,
(5) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, a compound having an epoxy group and an unsaturated double bond in one molecule is reacted with a part of the produced carboxylic acid. Hydroxyl group and carboxyl group-containing unsaturated polyester resin obtained,
(6) Reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and a compound having at least one alcoholic hydroxyl group in one molecule and one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group A carboxyl group-containing unsaturated polyester resin obtained by reacting a product with a saturated or unsaturated polybasic acid anhydride, and (7) a polyfunctional oxetane compound having at least two oxetane rings in one molecule. Examples thereof include a carboxyl group-containing unsaturated polyester resin obtained by reacting a carboxylic acid and reacting a saturated or unsaturated polybasic acid anhydride with a primary hydroxyl group in the resulting modified oxetane resin.
Among these, the carboxyl group-containing unsaturated polyester resin (4) derived from a polyfunctional epoxy compound is preferable because of good adhesion and the like.

  Furthermore, by using the linear polyfunctional epoxy compound (a) as listed below as the polyfunctional epoxy compound used for the production of the carboxyl group-containing unsaturated polyester resin of (4), TAB, CSP, It is possible to provide a thermosetting resin composition having excellent bending resistance and less warpage, and a cured coating film suitably used for a semiconductor carrier tape used for TCP and a flexible printed wiring board such as COF.

  That is, the carboxyl group-containing unsaturated polyester resin (A) is at least one selected from the group consisting of epoxy compounds represented by the following general formula (II), the following general formula (III), and the following general formula (V). Polyfunctional epoxy compound (a)

（式中、Ｒ^３，Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は水素原子又はグリシジル基を示し、ｎは１〜５０の値を示す。）

^(Wherein, R 3, ^{R 4} represents a hydrogen atom or a methyl group, ^{R 5} represents a hydrogen atom or a glycidyl radical, n denotes a value of 1-50.)

（式中、Ｍは下記一般式（IV）で表わされる基を示し、Ｒ^６は脂肪族又は芳香族多官能カルボン酸の残基を示し、ｍは１〜５０の値を示す。）

(In the formula, M represents a group represented by the following general formula (IV), R ⁶ represents an aliphatic or aromatic polyfunctional carboxylic acid residue, 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／又はベンゼン環を示し、Ｒ^９，Ｒ^１０は水素原子又はメチル基を示し、Ｒ^１１は水素原子又はグリシジル基を示し、ｋは０〜２５の値を示す。）

(Wherein R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or a benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, R ¹¹ represents a hydrogen atom or a glycidyl group, and k represents Shows values from 0 to 25.)

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

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樹脂である。

(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 reaction product of the unsaturated monocarboxylic acid (b) with a saturated and / or unsaturated polybasic acid anhydride (c).

The polyfunctional epoxy compound (a) represented by the general formula (II) is a bisphenol F type or bisphenol A type 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 polyfunctionalized bisphenol skeleton resin by dissolving a bifunctional epoxy compound in an aprotic polar solvent such as dimethyl sulfoxide and reacting an epihalohydrin and an alkali metal hydroxide as described later.
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, viscosity is increased, printability is lowered, solid content concentration is lowered, and it is difficult to obtain a sufficient film thickness, 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%, the crosslink density due to Michael addition decreases, and the coating properties such as water resistance decrease, 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 polyfunctional epoxy compound (a) represented by the general formula (III) comprises 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 a raw material, a linear epoxy compound having a terminal epoxy group obtained by alternately polymerizing using a known esterification catalyst as described later, a polyfunctional epoxy compound (a) represented by the general formula (II) In the same manner as above, it is dissolved in an aprotic polar solvent such as dimethyl sulfoxide and the like, and is polyfunctionalized by reacting an epihalohydrin and 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, viscosity is increased, printability is lowered, solid content concentration is lowered, and it becomes difficult to obtain a sufficient film thickness. 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%, the crosslink density due to Michael addition decreases, and the coating properties such as water resistance decrease, 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, 2-hydroxy-2-methylsuccinic acid and phthalic anhydride adduct, etc. Aliphatic or cycloaliphatic dicarboxylic acid compounds such as 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, adipic acid, muconic acid, suberic acid, and sebacic acid 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 polyfunctional epoxy compound (a) 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 one molecule. Using a bifunctional phenolic compound having two phenolic hydroxyl groups as a raw material, using a known etherification catalyst as described later, a linear form of a terminal epoxy group obtained by alternately polymerizing in a solvent or in the absence of a solvent By dissolving an epoxy compound in an aprotic polar solvent such as dimethyl sulfoxide, and reacting an epihalohydrin and an alkali metal hydroxide in the same manner as the polyfunctional epoxy compound (a) represented by the general formula (II). Is polyfunctionalized.

Examples of the bifunctional aromatic epoxy compound include biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, naphthalene-type dithiol having an aromatic ring represented by the following formulas (VI) to (IX). At least one bifunctional aromatic epoxy compound such as glycidyl ether is used. By using such a bifunctional aromatic epoxy compound as one monomer component in an alternating copolymer with a bifunctional phenol compound, an epoxy compound excellent in the strength, heat resistance, electrical insulation, etc. of the cured product is obtained. It is done.

（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のアルキル基を示し、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示し、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示す。）

(In the formula, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are the same or different and represent a hydrogen atom or an alkyl group 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 the biphenol type diglycidyl ether, trade name “Epicoat YL-6056” manufactured by Japan Epoxy Resin Co., Ltd., and as the bixylenol type diglycidyl ether, Japan Epoxy Bisphenol A type epoxy compounds 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 Resin Co., Ltd. Or a bisphenol F type epoxy compound such as “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc. or a bisphenol S type epoxy compound such as “Epicron EXA1514” manufactured by Dainippon Ink and Chemicals, Inc. , Naphthalene type jigli The Jill 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 used as the raw material for the polyfunctional epoxy compound (a) represented by the general formula (V) has a characteristic structure, has an aromatic ring to increase heat resistance, and has a symmetrical structure or Those having a rigid structure can be used. 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 unsaturated monocarboxylic acid (b) to be reacted with the linear polyfunctional epoxy compound (a) as described above include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, and α-cyanocinnamic acid. In addition to acid, β-styrylacrylic acid, etc., hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, di Examples thereof include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as pentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct. 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 unsaturated polyester resin (A) has an acid value of 30 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 unsaturated polyester resin (A) is less than 30 mgKOH / g, the crosslinking density due to the reaction with the oxirane ring is lowered, and the coating film properties such as solder heat resistance are lowered. On the other hand, if it exceeds 200 mgKOH / g, the crosslinking density due to the reaction with the oxirane ring is increased, it becomes hard, and the flexibility is lowered, which is not preferable.

  Examples of the resin (B) having two or more epoxy groups in one molecule include bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, cresol novolak type, and bisphenol A novolak. Type, biphenol type, bixylenol type, trisphenolmethane type glycidyl ethers; diglycidyl phthalate and other glycidyl esters; triglycidyl isocyanurate and tetraglycidyl metaxylylenediamine and other glycidyl amines; 3,4-epoxy Cyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate and other alicyclic epoxy resins; known and commonly used epoxy resins such as epoxidized polybutadiene can be used alone or in combination of two or more. . Of these, particularly preferred are triglycidyl isocyanurates (there are α and β isomers as structural isomers, although β isomers are particularly preferred), which are hardly soluble in organic solvents, and the like. Examples thereof include epoxidized polybutadiene having a large effect. The compounding ratio of these epoxy resins is 0.6 to 2.0 equivalents with respect to 1 equivalent of carboxyl groups of the carboxyl group-containing unsaturated polyester resin (A), It is preferable in terms of characteristics such as solder heat resistance.

Next, the amine-based active hydrogen compound (C) is a compound that is Michael-added to the ethylenically unsaturated group of the carboxyl group-containing unsaturated polyester resin (A) at the time of thermosetting. What is used as a basic amine hardening agent can be used. Specific examples include dicyandiamide; guanamines such as melamine, vinyltriazine, acetoguanamine, and benzoguanamine; organic acid hydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide. Among these, dicyandiamide and melamine are particularly preferable because they also have a rust preventive effect on the copper foil. You may use these individually or in mixture of 2 or more types.
The compounding amount of these amine-based active hydrogen compounds (C) is 1 equivalent of active hydrogen of amine-based active hydrogen compound (C) with respect to 1 equivalent of ethylenically unsaturated groups of the carboxyl group-containing unsaturated polyester resin (A). It is preferable that these amine-based active hydrogen compounds react with the resin (B) having two or more epoxy groups in one molecule or form a chelate with copper foil. 0.1 to 10% by mass, preferably 0.2 to 5% by mass.

The phosphoric acid amide (D) represented by the following general formula (I), which is a feature of the halogen-free and flame-retardant 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のアルキル基を示す。）

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フェニル基、又はその芳香環の水素原子１〜２個が炭素数１〜４のアルキル基に置換されたジフェニルホスフィニルハライド類と、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。

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

A phenyl group such as diphenylphosphinyl chloride, diphenylphosphinyl bromide, di-3,5-xylenylphosphinyl chloride, or 1 to 2 hydrogen atoms of the aromatic ring is an alkyl group having 1 to 4 carbon atoms. It can be synthesized by dissolving substituted diphenylphosphinyl halides 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 has extremely low hydrolyzability as compared with the phosphoric acid esters, and is an alkali such as a plating treatment when producing a printed wiring board. Alternatively, stable flame retardancy and electrical insulation can be maintained without hydrolysis even by chemical treatment with acid or subsequent heat treatment.
Moreover, since melting | fusing point is also high, it does not melt | dissolve at the time of thermosetting and does not contaminate copper foil etc. Further, since the molecule contains a nitrogen atom, a phosphazene ring or the like is formed at the time of combustion, and the flame retardancy imparting effect is higher than that of the phosphate ester.
As a compounding quantity of the phosphoric acid amide (D) represented by the said general formula (I), 5-50 mass% in the thermosetting resin composition of this invention, Preferably it is 10-40 mass%, More preferably, it is 20 -40 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.

In addition, the thermosetting resin composition of the present invention, if necessary, for the purpose of improving properties such as adhesion, hardness, heat resistance, etc., known and commonly used materials such as barium sulfate, talc, silica, clay, aluminum hydroxide and the like. An inorganic filler can be blended, and the blending amount thereof is suitably 60% by mass or less, preferably 5 to 40% by mass in the composition. If the blending amount of the inorganic filler exceeds the above ratio, the bending resistance and folding resistance of the cured coating film are lowered, which is not preferable. Further, if necessary, known and commonly used color pigments (eg, titanium oxide, carbon, phthalocyanine blue, phthalocyanine green, disazo yellow, etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents, silane coupling agents Etc. can be added.
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 thermosetting resin composition having the composition as described above is applied to a printed wiring board or a tape carrier package on which a circuit is formed by a screen printing method, for example, by heating to a temperature of 120 to 180 ° C. and thermosetting it. A cured coating film excellent in adhesion to the substrate, plating resistance, solder heat resistance, electrical insulation, and the like is formed.

  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 of carboxyl group-containing unsaturated polyester resin (A)>
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 210 parts of cresol novolac type epoxy resin (Epiclon N-680, manufactured by Dainippon Ink and Chemicals, epoxy equivalent = 210) and carbitol acetate 109 .7 parts 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 unsaturated polyester 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 of carboxyl group-containing unsaturated polyester resin (A)>
A flask equipped with a stirrer, a condenser and a thermometer was charged with 380 parts of bisphenol F type epoxy resin (epoxy equivalent = 950, softening point 85 ° C., average polymerization degree n = 6.2) and 925 parts of epichlorohydrin, and dimethyl sulfoxide. After dissolving in 462.5 parts, 60.9 parts (1.5 mol) of 98.5% pure sodium hydroxide was added over 100 minutes at 70 ° C. with stirring. 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 was added 140 parts of tetrahydrophthalic anhydride, heated to 90 ° C., and reacted until the solid content acid value reached 100 mgKOH / g. 62.5 of carboxyl group-containing unsaturated polyester photocurable resin (A) was obtained. % Solution was obtained. Hereinafter, this solution is referred to as A-2 varnish.

<Synthesis example 3 of carboxyl group-containing unsaturated polyester resin (A)>
In a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, 172 parts of 1,4-cyclohexanedicarboxylic acid and epoxide equivalent = 176 hydrogenated bisphenol A diglycidyl ether (manufactured by Japan Epoxy Resin, “YX8000”) ) 880 parts were charged and stirred at 100 ° C. under a nitrogen atmosphere. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C., and the reaction was continued for about 90 minutes while maintaining the temperature at 150 ° C., and a linear epoxy having an epoxy equivalent of 438 g / equivalent was obtained. A compound was obtained.
Next, the temperature in the flask was cooled to 70 ° C. or lower, 780 parts of epichlorohydrin and 635 parts of dimethyl sulfoxide were added, and the temperature was raised to 70 ° C. with stirring and held. Thereafter, 150 parts of 96% pure sodium hydroxide was added in portions over 90 minutes, followed by further reaction for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were distilled under reduced pressure of 120 ° C. and 50 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain a polyfunctional epoxy compound (a) represented by the general formula (III) having an epoxy equivalent of 247.
Next, 494 parts of the polyfunctional epoxy compound (a) is put into a flask equipped with a stirrer, a condenser tube and a thermometer, and 563.5 parts of carbitol acetate is added, dissolved by heating, and 0.46 part of methyl hydroquinone. And 1.38 parts of triphenylphosphine were added and heated to 95 to 105 ° C., 350 parts of acrylic acid was gradually added dropwise and reacted for 20 hours. The reaction product was cooled to 80 to 90 ° C., 300 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, the acid value and total acid value of the reaction solution are measured by potentiometric titration, followed by the addition rate obtained, and the reaction rate is 95% or more as the end point.
The carboxyl group-containing unsaturated polyester resin (A) varnish thus obtained had a nonvolatile content of 67% and a solid acid value of 89.2 mgKOH / g. Hereinafter, this carboxyl group-containing unsaturated polyester resin (A) varnish is referred to as A-3 varnish.

<Synthesis example 4 of carboxyl group-containing unsaturated polyester resin (A)>
In a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, 203 parts of 1,5-dihydroxynaphthalene and 1097 parts of Epicron-840 of bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180) Charge and dissolve at 120 ° C. under stirring in a nitrogen atmosphere. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the flask was raised to 150 ° C., and the reaction was allowed to proceed for about 90 minutes while maintaining the temperature at 150 ° C. to obtain a bifunctional epoxy compound having an epoxy equivalent of 365. Obtained.
Next, the temperature in the flask is cooled to 70 ° C. or lower, 2058 parts of epichlorohydrin and 1690 parts of dimethyl sulfoxide are added, and the temperature is raised to 70 ° C. with stirring and maintained. Thereafter, 122 parts of 96% sodium hydroxide are added in portions over 90 minutes. After the addition, the reaction is further continued for 3 hours. After completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide are distilled at 120 ° C. under reduced pressure of 50 mmHg, and the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain a polyfunctional epoxy compound (a) represented by the general formula (V) having an epoxy equivalent of 275. When the obtained polyfunctional epoxy compound (a) is calculated from the epoxy equivalent, about 0.82 of 1.71 alcoholic hydroxyl groups in the bifunctional epoxy compound are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 48%. Next, 347 parts of the polyfunctional epoxy compound (a) is put into a flask equipped with a stirrer, a condenser tube and a thermometer, 401 parts of carbitol acetate is added, and heated to dissolve, 0.46 parts of methylhydroquinone and triphenyl are added. 1.38 parts of phosphine was added and heated to 95 to 105 ° C., 91 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 163 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for 8 hours. In the reaction, the acid value and total acid value of the reaction solution are measured by potentiometric titration, followed by the addition rate obtained, and the reaction rate is 95% or more as the end point. The carboxyl group-containing unsaturated polyester resin (A) varnish thus obtained had a nonvolatile content of 60% and a solid acid value of 100 mgKOH / g. Hereinafter, this reaction solution is referred to as A-4 varnish.

<Examples 1-4 and Comparative Examples 1-2>
The compounding component shown in Table 1 using each varnish obtained in the synthesis example was kneaded with a three-roll mill to obtain a thermosetting resin composition. The evaluation results of each thermosetting resin composition are shown in Table 2.

なお、上記表２中の性能試験の方法は、以下の通りである。

The performance test method in Table 2 is as follows.

Performance evaluation:
(1) Flame Retardant A non-halogen flame retardant substrate RO-67G (0.2 mmt material) manufactured by Hitachi Chemical Co., Ltd. was coated on the entire surface by screen printing at 20 μm on one side and heated at 150 ° C. for 30 minutes in a hot air circulation drying oven. Cured. 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 Each thermosetting resin composition was pattern-printed on a printed wiring board on which a circuit was formed so that the cured coating film had a thickness of about 20 μm, and cured at 150 ° C. for 30 minutes. 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

(5) Folding resistance Each of the thermosetting resin compositions of Examples 2 to 4 above was printed on the entire surface of a Kapton material (thickness 50 μm) by screen printing and cured at 150 ° C. for 30 minutes (dry film). Thickness 20 μm). The obtained cured film was bent 180 ° outside and evaluated according to the following criteria.
○: The cured film has no cracks △: The cured film has some cracks ×: The cured film has cracks

(6) Warpage Each of the thermosetting resin compositions of Examples 2 to 4 was screen-printed on a Kapton material (150 × 110 mm, thickness 25 μm) and cured at 150 ° C. for 30 minutes ( Dry film thickness 20 μm). After cooling, the warpage of the obtained cured coating film was evaluated according to the following criteria.
○: No warpage
Δ: Slightly warped
×: Warping

As is apparent from the results shown in Table 2, the cured coating film obtained from the thermosetting resin composition of the present invention is non-halogen and has the same flame retardancy as the cured product using the halogen-containing epoxy resin of Comparative Example 3. And has excellent chemical resistance such as acid resistance and alkali resistance. 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 (6)

(A) a carboxyl group-containing unsaturated polyester resin having one or more carboxyl groups and ethylenically unsaturated groups in one molecule;
(B) a resin having two or more epoxy groups in one molecule;
(C) an amine-based active hydrogen compound,
And (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 shows a hydrogen atom or a C1-C4 alkyl group.)

A thermosetting resin composition comprising: The carboxyl group-containing unsaturated polyester resin (A) is at least one selected from the group consisting of the following general formula (II), the following general formula (III), and the epoxy compound represented by the following general formula (V). Functional epoxy compound (a)

^(Wherein, R 3, ^{R 4} represents a hydrogen atom or a methyl group, ^{R 5} represents a hydrogen atom or a glycidyl radical, n denotes a value of 1-50.)

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

(Wherein R ⁷ and R ⁸ represent a divalent cyclohexane ring and / or a benzene ring, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, R ¹¹ represents a hydrogen atom or a glycidyl group, and k represents Shows values 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.)

The resin obtained by reacting a saturated and / or unsaturated polybasic acid anhydride (c) with a reaction product of a monocarboxylic acid (b) and an unsaturated monocarboxylic acid (b). Thermosetting resin composition. The thermosetting resin composition according to claim 1 or 2, wherein the resin (B) having two or more epoxy groups in one molecule is a resin containing epoxidized polybutadiene. The thermosetting resin composition according to any one of claims 1 to 3, wherein the amine-based active hydrogen compound (C) is melamine and / or dicyandiamide. The thermosetting resin composition according to any one of claims 1 to 4, wherein the phosphoric acid amide compound (D) is contained in the composition in an amount of 5 to 50% by mass. A cured coating film obtained by curing the thermosetting resin composition according to any one of claims 1 to 5 by heating.