JP2023090561A - Resin composition, curable composition, cured product, insulating material, and resist member - Google Patents

Abstract

To provide a resin composition capable of improving elongation, adhesion and low dielectric characteristics of a cured product obtained therefrom in a well-balanced manner, and to provide a cured product, an insulating material, and a resist member.SOLUTION: The present disclosure is the resin composition containing: a phosphorus-containing active ester which uses an aromatic compound having two or more carboxyl groups and/or an acid halide or esterified product thereof (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing aliphatic compound (D) as reaction raw materials; and a resin having an acid group and a polymerizable unsaturated group.SELECTED DRAWING: None

Description

The present disclosure relates to resin compositions, curable compositions, cured products, insulating materials, and resist members.

Solder resist is a material used to form a coating that semi-permanently prevents solder from sticking to areas other than the mounting area when mounting and soldering electronic components on a printed wiring board, and also prevents oxidation or corrosion of wiring. is widely used. As a technique for forming such a solder resist pattern, an alkali development type liquid photoresist method, which can accurately form a fine pattern, has become mainstream, especially from consideration of the environment.
In recent years, in order to realize higher density of electronic components, printed wiring boards are becoming finer (finer), multi-layered, and single-board, and mounting methods are also shifting to surface mounting technology (SMT). is transitioning. Therefore, solder resist films are also required to be finer, have higher Tg, higher resolution, higher precision, and higher reliability. Furthermore, along with the increase in the speed of transmission signals, there is a demand in the solder resist market for technology exhibiting a low dielectric constant and a low dielectric loss tangent that reduces time delay for the use of high frequencies (gigahertz band).
For such alkali-developable liquid photoresists, a reaction product (acid-pendant-type epoxy acrylate) obtained by reacting a novolac-type epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride is widely used. (see Patent Document 1). However, epoxy acrylate is known to have a high dielectric constant due to the formation of hydroxyl groups when the epoxy resin and unsaturated monocarboxylic acid are reacted. Therefore, for example, Patent Document 2 discloses a technique for improving heat resistance, dielectric loss tangent, and water resistance using a photosensitive resin composition containing an active ester curing agent and a carboxyl group-containing radically polymerizable compound. It is

Japanese Patent No. 6094271 JP-A-2004-169021

However, the techniques of Patent Documents 1 and 2 do not consider the elongation and adhesiveness of the cured product formed from the photosensitive resin composition.
Therefore, the present disclosure provides a resin composition that can improve elongation, adhesion and low dielectric properties in a well-balanced manner in the resulting cured product, a curable composition containing the resin composition, and the cured product. An object of the present invention is to provide a resin composition, a curable composition, a cured product, an insulating material, and a resist member obtained by using a curable composition.

In order to solve the above problems, as a result of extensive studies, the present inventors have found that by using a composition containing a specific phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group, The inventors have found that elongation, adhesion, and low dielectric properties can be improved in a well-balanced manner in the cured product obtained by the method, and have completed the present invention.

The resin composition of the present disclosure includes an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol aromatic compound (C ) and an ether bond-containing aliphatic compound (D) as reaction raw materials, and a resin having an acid group and a polymerizable unsaturated group.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide a resin composition that has excellent adhesiveness and can provide a cured product having excellent dielectric properties and elongation. Moreover, according to the present disclosure, it is possible to provide a curable composition containing such a resin composition, a cured product thereof, and an insulating material and a resist material using such a cured product.

1 is a GPC chart of diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. FIG. 1 is a ¹ H-NMR chart of diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. FIG. 1 is an FD-MS spectrum chart of diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. FIG. 1 is a GPC chart of a phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. FIG. 2 is a ¹³ C-NMR chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. FIG. 2 is an FD-MS spectrum chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. FIG. 1 is a GPC chart of phosphorus-containing active ester (1) obtained in Synthesis Example 3. FIG. 13 is a ¹³ C-NMR chart of the phosphorus-containing active ester (1) obtained in Synthesis Example 3. FIG. 4 is an FD-MS spectrum chart of the phosphorus-containing active ester (1) obtained in Synthesis Example 3. FIG. 1 is a GPC chart of a phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) obtained in Synthesis Example 4. FIG. 4 is a GPC chart of the phosphorus-containing active ester (2) obtained in Synthesis Example 5. FIG. 1 is a GPC chart of a phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ) obtained in Synthesis Example 6. FIG. 4 is a GPC chart of the phosphorus-containing active ester (3) obtained in Synthesis Example 7. FIG. 2 is a GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-PPQ) obtained in Synthesis Example 8. FIG. 4 is a GPC chart of the phosphorus-containing active ester (4) obtained in Synthesis Example 9. FIG. 1 is a GPC chart of Comparative Intermediate (1) obtained in Comparative Synthesis Example 1. FIG. 1 is a GPC chart of a phosphorus atom-containing compound (1) obtained in Comparative Synthesis Example 2. FIG. 1 is a GPC chart of a phosphorus atom-containing ester compound (1) obtained in Comparative Synthesis Example 3. FIG.

Hereinafter, embodiments of the present disclosure (hereinafter referred to as "present embodiments") will be described in detail. can be implemented.

[Resin composition]
The present disclosure is a resin composition containing a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group. The phosphorus-containing active ester includes an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A), an aromatic monoalcohol (B), and a phosphorus-containing polyhydric alcohol compound ( C) and an ether bond-containing aliphatic compound (D) are essential reaction raw materials.
This makes it possible to form a cured product with improved elongation, adhesion and low dielectric properties in a well-balanced manner.

In the resin composition of the present disclosure, the content of the phosphorus-containing active ester is from 90 to 90 with respect to the total amount of the resin composition (100% by mass), from the viewpoint of improving the elongation, adhesion and low dielectric properties in a well-balanced manner. A range of 10% by weight is preferred. The upper limit or lower limit of the content of the phosphorus-containing active ester is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 90% by mass or less, and 80% by mass or less. More preferably, 70% by mass or less is even more preferable.
Moreover, in the resin composition of the present disclosure, the content of the resin having an acid group and a polymerizable unsaturated group is preferably in the range of 90 to 10% by mass with respect to the total amount (100% by mass) of the resin composition. In addition, the upper limit or lower limit of the content of the resin having an acid group and a polymerizable unsaturated group is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and 90% by mass. The following is preferable, 80% by mass or less is more preferable, and 70% by mass or less is even more preferable.

In the resin composition of the present embodiment, the mass ratio of the solid content of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group [(phosphorus-containing active ester) / (acid group and polymerizable unsaturated group resin)] is preferably in the range of 5/95 to 50/50 from the viewpoint of improving elongation, adhesion and low dielectric properties in a well-balanced manner. From the same point of view, the upper or lower limit of the mass ratio [(phosphorus-containing active ester) / (resin having an acid group and a polymerizable unsaturated group)] is more preferably 10/90 or more, and 20/80. It is more preferably 40/60 or less.

The resin composition in this embodiment may further contain an optional additive component as an optional component.
Moreover, the resin composition in this embodiment may be substantially composed only of the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and optional additive components. Furthermore, the resin composition of the present embodiment may be composed only of a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group.
The total content of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group in the total amount (100% by mass) of the resin composition of the present embodiment improves elongation, adhesion and low dielectric properties in a well-balanced manner. 40% by mass or more, more preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of
The above-mentioned "consisting only of a phosphorus-containing active ester, a resin having an acid group and a polymerizable unsaturated group, and an optional additive component" is preferably 80 to 100% by mass with respect to the total amount (100% by mass) of the resin composition. , or at least 90 to 95% by mass of a phosphorus-containing active ester and a resin component having an acid group and a polymerizable unsaturated group, or a resin having a phosphorus-containing active ester, an acid group and a polymerizable unsaturated group, and an optional additive component means that
The resin composition of the present embodiment contains inevitable impurities in addition to the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and the optional additive components, as long as the effects of the present disclosure are not impaired. You can
Hereinafter, after explaining the main terms described in the present specification, each component contained in the resin composition in the present embodiment, a phosphorus-containing active ester, a resin having an acid group and a polymerizable unsaturated group, and The optional additive component will be explained.

(Explanation of terms)
Unless otherwise stated herein, the following terms are applicable.
The "aromatic group" used herein preferably has an aromatic ring with 3 to 30 carbon atoms, more preferably an aromatic ring with 4 to 26 carbon atoms. The "aromatic group" used herein means that the hydrogen atom of the aromatic ring in the aromatic group is a substituent such as an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. It may be substituted by a group or a halogen atom. In addition, the "aromatic group" includes a heteroaromatic group, and is substituted with -O-, -S- or -N= so that -CH ₂ - or -CH= in the "aromatic group" are not adjacent to each other. may
Types of the aromatic ring include, for example, monocyclic aromatic rings, condensed aromatic rings, and ring-assembled aromatic rings. Examples of the monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine and triazine. Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the ring-assembled aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. In addition, the hydrogen atom of the aromatic ring in the aromatic group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
In addition, a monovalent aromatic group refers to a group in which one hydrogen atom is removed from the "aromatic group", and a divalent aromatic group refers to a group in which two hydrogen atoms are removed from the "aromatic group". A trivalent to hexavalent aromatic group refers to a group in which 3 to 6 hydrogen atoms are removed from an "aromatic group".
The "aryl group" used herein includes, for example, phenyl group, naphthyl group, phenalenyl group, phenanthrenyl group, anthryl group, azulenyl group, indenyl group, indanyl group, tetralinyl group and the like. In addition, the "aryl group" is a hydrogen atom of an aromatic ring in the aryl group, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. good too. In addition, the "arylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above "aryl group".
As used herein, the "aralkyl group" includes, for example, a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group and the like. A hydrogen atom of an aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. In addition, the "aralkylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above "aralkyl group".
The "alkyl group" used herein is, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-) heptyl group, (n-) octyl group, (n-) nonyl group, (n-) decyl group, (n-) undecyl group, (n-) dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group or cyclononyl group. In addition, the "alkylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above "alkyl group".
The "alkenyl group" used herein includes ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentynyl, hexynyl, vinyl, allyl, and isopropenyl groups. In addition, the "alkenylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above "alkenyl group".
The "alkoxy group" used herein includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, and the like. mentioned.
The "halogen atom" as used herein includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The "linear or branched alkylene group" used herein includes, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1 , 1-dimethylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group , undecylene group, dodecylene group, and the like.
The "linear or branched alkylene ether group" used herein is, for example, an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxy(1-methylmethylene) group, an oxy(1,1-dimethylmethylene) ) group, oxy (1-methylethylene) group, oxy (1,1-dimethylethylene) group, oxy (1,2-dimethylethylene) group, oxybutylene group, oxy (1-methylpropylene) group, oxy (2 -methylpropylene) group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylene group, oxyundecylene group, oxydecylene group and the like.
A "monovalent hydrocarbon group" as used herein includes linear, branched or cyclic saturated hydrocarbon, unsaturated hydrocarbon, or aromatic groups. For example, the "monovalent hydrocarbon group" is one group selected from the group consisting of an alkyl group (e.g., the alkyl group described above), an alkyl group, an alkenyl group, an aryl group, an aralkyl group and an alkoxy group, and One or more —CH ₂ — in the group may be substituted with —O— or —S— so that they are not adjacent to each other, or one or more —CH ₂ —CH ₂ — in the alkyl group may -CH=CH- may be substituted so that they are not adjacent to each other. The hydrocarbon group may be linear or branched, preferably a group having 1 to 20 carbon atoms, and may be an alkyl group having 1 to 20 carbon atoms.
A "divalent hydrocarbon group" as used herein includes linear, branched or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, one group selected from the group consisting of an alkylene group (e.g., the linear or branched alkylene group), an alkenylene group, an arylene group, an aralkylene group and an alkylene ether group, and may be substituted with -O- or -S- such that one or more -CH ₂ - are not adjacent to each other, or one or more -CH ₂ -CH ₂ - in the alkylene group are not adjacent to each other such as -CH=CH- may be substituted. The hydrocarbon group may be linear or branched, preferably a group having 1 to 20 carbon atoms, and may be an alkylene group having 1 to 20 carbon atoms.
The "trivalent to hexavalent hydrocarbon group" used herein includes linear, branched or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, from one group selected from the group consisting of an alkyl group (e.g., the above alkyl group), an alkyl group, an alkenyl group, an aryl group, an aralkyl group and an alkoxy group, two to five hydrogen atoms at arbitrary positions One or more —CH ₂ — in the removed group and the group from which the hydrogen atom has been removed may be substituted with —O— or —S— so that they are not adjacent to each other, or One or more -CH ₂ -CH ₂ - may be replaced with -CH=CH- such that they are not adjacent to each other. Also, the hydrocarbon group may be linear or branched and may have 1 to 20 carbon atoms.
As used herein, "(meth)acrylate" means acrylate and/or methacrylate. Moreover, in this specification, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, in this specification, "(meth)acryl" means acryl and/or methacryl.
As used herein, the term "carbonate compound" refers to an aliphatic hydrocarbon having a carbonate group (--O--(C=O)--O--), for example, an alkylene carbonate having 1 to 5 carbon atoms (ethylene carbonate, carbonic acid propylene or butylene carbonate).

(Phosphorus-containing active ester)
The phosphorus-containing active ester in this embodiment is one of the essential components in the resin composition of this embodiment. Further, the phosphorus-containing active ester includes an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A), an aromatic monoalcohol (B), and a phosphorus-containing polyhydric alcohol compound (C ) and the ether bond-containing aliphatic compound (D) as essential reaction raw materials.
If necessary, the reaction raw materials include an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A), an aromatic monoalcohol (B), and a phosphorus-containing polyhydric alcohol compound (C). , or a compound that exhibits reactivity with the ether bond-containing aliphatic compound (D).
In principle, the phosphorus-containing active ester obtained from the reaction raw materials has no or almost no hydroxyl groups in its molecule. However, a compound having a hydroxyl group may be included as a by-product of the reaction product to the extent that the effects of the present disclosure are not impaired.

In the present specification, "an aromatic compound having two or more carboxyl groups and/or acid halides or esters thereof (A)" is hereinafter simply referred to as "aromatic polycarboxylic acids (A)". There is
Hereinafter, aromatic polycarboxylic acids (A), aromatic monoalcohols (B), phosphorus-containing polyhydric alcohol compounds (C), and ether bond-containing aliphatic compounds (D), which are reaction raw materials for phosphorus-containing active esters, are described below. Before describing, the structure and properties of the phosphorus-containing active ester will be detailed.

<Structure of phosphorus-containing active ester>
From the viewpoint of the chemical structure, the phosphorus-containing active ester of the present embodiment includes the residue of an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A), and an aromatic monoalcohol (B ), the residue of the phosphorus-containing polyhydric alcohol compound (C), and the residue of the ether bond-containing aliphatic compound (D).
More specifically, the phosphorus-containing active ester of the present embodiment is an ester bond derived from the carboxylic acid or its acid halogen group in the aromatic polycarboxylic acids (A) and the phenolic hydroxyl group in the aromatic monoalcohol (B). , and an ether bond derived from the hydroxyl group in the phosphorus-containing polyhydric alcohol compound (C) and the ether group in the ether bond-containing aliphatic compound (D).

In the present specification, "an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A)" refers to an atomic group containing a carbonyl group (-C (=O) -X ( X represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent hydrocarbon group.)) is a compound having an aromatic group in which two or more are bonded. In the present specification, "the residue of an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A)" refers to a phosphorus-containing active ester produced by reaction or polymerization. , refers to the partial structure of an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A) that remains in the phosphorus-containing active ester molecule due to the reaction or polymerization. It is composed of a formed chemical bond and a group derived from an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A) other than the chemical bond.
In addition, the term "derived group" as used herein refers to a partial structure other than the chemical bond structure involved in the reaction or polymerization in the product compound formed by the reaction or polymerization. Therefore, the "group derived from an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A)" refers to an aromatic compound having two or more carboxyl groups and/or an acid halide or A divalent or higher valent group excluding a carbonyl group-containing atomic group (-C(=O)-X (X represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent hydrocarbon group) from the ester (A) represents a group, which can be, for example, a divalent or higher aromatic group.

で表すことができるが、この場合、Ｑ^ａ１は、２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、Ｘは、水素原子、ハロゲン原子、水酸基又は一価の炭化水素基を表し、ｎ^ａ１は２以上６以下の整数を表し、破線部分が、２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）の残基を表す。 An aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A) has the following general formula (A):

In this case, Q ^a1 represents an aromatic compound having two or more carboxyl groups and / or a group derived from an acid halide or ester thereof (A), X is a hydrogen atom, a halogen represents an atom, a hydroxyl group, or a monovalent hydrocarbon group, n ^a1 represents an integer of 2 or more and 6 or less, and the dashed line indicates an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof ( A) represents the residue.

で表すことができるが、この場合、Ａｒ^ｂ１が、芳香族モノアルコール（Ｂ）由来の基を表し、芳香族モノアルコール（Ｂ）から水素原子又は水酸基を除いた一価の基であり、破線部分が、芳香族モノアルコール（Ｂ）の残基を表す。 The term "residue of aromatic monoalcohol (B)" as used herein refers to a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from aromatic monoalcohol (B). "Aromatic monoalcohol (B)" has the following general formula (b1):

In this case, Ar ^b1 represents a group derived from the aromatic monoalcohol (B), and is a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from the aromatic monoalcohol (B), and a dashed line The moiety represents the residue of the aromatic monoalcohol (B).

で表すことができるが、この場合、Ａ^ｃ１はリン含有多価アルコール化合物（Ｃ）由来の基を表し、リン含有多価アルコール化合物（Ｃ）から水素原子又は水酸基を除いたｎ^ｃ１価の基であり、具体的には、リン原子を含有する二価～六価の炭化水素基を表し、ｎ^ｃ１は２以上６以下の整数を表す。ｎ^ｃ１は、２であることが好ましい。 The term "residue of the phosphorus-containing polyhydric alcohol compound (C)" used herein refers to a divalent or higher polyvalent group obtained by removing two or more hydrogen atoms or hydroxyl groups from the phosphorus-containing polyhydric alcohol compound (C). "Phosphorus-containing polyhydric alcohol compound (C)" has the following general formula (c1):

In this case, A ^c1 represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and an n ^c monovalent group obtained by removing a hydrogen atom or a hydroxyl group from the phosphorus-containing polyhydric alcohol compound (C) Specifically, it represents a divalent to hexavalent hydrocarbon group containing a phosphorus atom, and n ^c1 represents an integer of 2 or more and 6 or less. n ^c1 is preferably two.

［上記一般式（ｄ１）中、Ｒ^ｄ１及びＲ^ｄ２はそれぞれ独立して、水素原子、アルキル基又はアルキレン基を表し、Ｒ^ｄ１又はＲ^ｄ２の一方がアルキレン基の場合は他方もアルキレン基であり、かつＲ^ｄ１及びＲ^ｄ２が互いに結合して環構造を形成してもよく、前記アルキル基又はアルキレン基中の１以上の－ＣＨ_２－は、互いに隣接しないよう、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－又は－Ｓ－に置換されてもよい。］で表すことができる。なお、上記一般式（ｄ１）中の破線部は、Ｒ^ｄ１とＲ^ｄ２とが互いに結合している形態及びＲ^ｄ１とＲ^ｄ２とが結合していない形態との両方を表す。
エーテル結合含有脂肪族化合物（Ｄ）としては、アルキレンオキサイド（例えばグリシジルエーテル）又はカーボネート基（－Ｏ－（Ｃ＝Ｏ）－Ｏ－）を含有する化合物などが挙げられる。具体的には、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等のエポキシ基を有する化合物や炭酸エチレン、炭酸プロピレン、炭酸ブチレン等のカーボネート類、アルキレンポリオール類が挙げられる。
また、本明細書においては、Ｒ^ｄ１及びＲ^ｄ２を合わせて、エーテル結合含有脂肪族化合物（Ｄ）由来の基を表す。例えば、リン含有活性エステルが一般式（１）で表される場合、当該一般式（１）中の－Ｒ^１－はそれぞれ独立して、－Ｒ^ｄ１－Ｒ^ｄ２－又は－Ｒ^ｄ２－Ｒ^ｄ１－でありうる。同様に、一般式（１）中の－Ｒ^２－はそれぞれ独立して、－Ｒ^ｄ１－Ｒ^ｄ２－又は－Ｒ^ｄ２－Ｒ^ｄ１－でありうる。
エーテル結合含有脂肪族化合物（Ｄ）を上記一般式（ｄ１）で表す場合、エーテル結合含有脂肪族化合物（Ｄ）由来の基は、上記一般式（ｄ１）で表されるエーテル結合含有脂肪族化合物（Ｄ）において酸素原子とＲ^ｄ１又はＲ^ｄ２の少なくとも一方との結合を切断した基であり、－Ｒ^ｄ１－Ｒ^ｄ２－又は－Ｒ^ｄ２－Ｒ^ｄ１－で表される。 The "residue of the ether bond-containing aliphatic compound (D)" in the present specification is bivalent or more in which one or more ether bonds present in the ether bond-containing aliphatic compound (D) are cleaved at least one location More specifically, at least one oxygen atom in the ether bond-containing aliphatic compound (D) and two carbon atoms (or one of which may be a hydrogen atom) bonded to the oxygen atom. A divalent or higher group in which at least one of two bonds (=ether bond) is cleaved.
The "ether bond-containing aliphatic compound (D)" has the following general formula (d1):

[In the above general formula (d1), R ^d1 and R ^d2 each independently represent a hydrogen atom, an alkyl group or an alkylene group, and when one of R ^d1 and R ^d2 is an alkylene group, the other is also an alkylene group. , and R ^d1 and R ^d2 may be bonded to each other to form a ring structure, and one or more —CH ₂ — in the alkyl group or alkylene group are not adjacent to each other, —O—, —C ( =O)-, -C(=O)-O- or -S- may be substituted. ]. The dashed line in the general formula (d1) represents both a form in which ^Rd1 and ^Rd2 are bonded together and a form in which ^Rd1 and ^Rd2 are not bonded.
Examples of the ether bond-containing aliphatic compound (D) include compounds containing an alkylene oxide (eg glycidyl ether) or a carbonate group (--O--(C=O)--O--). Specific examples include compounds having an epoxy group such as ethylene oxide, propylene oxide and butylene oxide, carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate, and alkylene polyols.
In the present specification, R ^d1 and R ^d2 together represent a group derived from the ether bond-containing aliphatic compound (D). For example, when the phosphorus-containing active ester is represented by general formula (1), each —R ¹ — in general formula (1) is independently —R ^d1 —R ^d2 — or —R ^d2 —R ^d1 - can be. Similarly, -R ² - in general formula (1) can each independently be -R ^d1 -R ^d2 - or -R ^d2 -R ^d1 -.
When the ether bond-containing aliphatic compound (D) is represented by the general formula (d1), the group derived from the ether bond-containing aliphatic compound (D) is an ether bond-containing aliphatic compound represented by the general formula (d1) A group obtained by cutting the bond between the oxygen atom and at least one of R ^d1 and R ^d2 in (D), and is represented by -R ^d1 -R ^d2 - or -R ^d2 -R ^d1 -.

In the present specification, values such as “monovalent” or “bivalent” simply indicate the number of bonds, and correspond to the number of ester bonds or ether bonds contributed by one molecule of each compound.

Further, the groups derived from the aromatic polycarboxylic acids (A) in the phosphorus-containing active ester may be divalent to hexavalent. In other words, in the phosphorus-containing active ester, the aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A) has a structure that directly or indirectly contributes to the ester bond. may be
Similarly, the group derived from the phosphorus-containing polyhydric alcohol compound (C) in the phosphorus-containing active ester may be divalent to hexavalent. In other words, in the phosphorus-containing active ester, two to six hydroxyl groups contained in one molecule of the phosphorus-containing polyhydric alcohol compound (C) have a structure that directly or indirectly contributes to an ester bond. good.

（上記一般式（ｉ）中、Ａｒ^ｂ１は芳香族モノアルコール（Ｂ）由来の基を表し、例えば、一価の芳香族基であり、Ｑ^ａ１は２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、例えば、二価の芳香族基であり、上記一般式（ｉ）中の＊は他の原子との結合手を表す。）
また、前記同一又は異なる芳香環は、２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）あるいは芳香族モノアルコール（Ｂ）の分子内の芳香族環に対応する。
剛直なメソゲン骨格である芳香族環と、柔軟なセグメントであるアルキレン鎖とがリン含有活性エステルの同一分子内に一定の規則性（繰返し単位）をもって共存することにより、樹脂組成物全体として難燃性を示し、かつ伸度、密着性及び低誘電特性により優れた硬化物を形成できる。 <<Preferred Form of Phosphorus-Containing Active Ester>>
More specifically, the phosphorus-containing active ester of the present embodiment includes a partial structure represented by the following general formula (i), in which the same or different aromatic rings are linked via an ester bond, and a phosphorus-containing poly Residue of the hydric alcohol compound (C) (e.g., a divalent to hexavalent hydrocarbon group (alkylene chain, alkyleneoxy chain, aromatic group) having a phosphorus atom and having a carbon atom and a hydrogen atom (alkylene chain, alkyleneoxy chain, aromatic group), and an ether and the residue of the bond-containing aliphatic compound (D) can have a chemical structure linked to.

(In the above general formula (i), Ar ^b1 represents a group derived from the aromatic monoalcohol (B), for example, a monovalent aromatic group, and Q ^a1 is an aromatic compound having two or more carboxyl groups and / or a group derived from its acid halide or ester (A), such as a divalent aromatic group, * in the above general formula (i) represents a bond with another atom.)
In addition, the same or different aromatic ring corresponds to an aromatic ring in the molecule of an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A) or aromatic monoalcohol (B). do.
The aromatic ring, which is a rigid mesogenic skeleton, and the alkylene chain, which is a flexible segment, coexist in the same molecule of the phosphorus-containing active ester with a certain regularity (repeating unit), so that the resin composition as a whole is flame retardant. It is possible to form a cured product excellent in elongation, adhesion and low dielectric properties.

（上記一般式（Ｊ－１）中、Ａはリン含有多価アルコール化合物（Ｃ）由来の２価～４価の基を表し、破線はそれぞれ独立して、不在であるか又は単結合である。）

（上記一般式（Ｊ－２）中、Ｒ^１は、エーテル結合含有脂肪族化合物（Ｄ）由来の基を表し、ｙ^１は１以上の平均繰り返し数を表す。）

（上記一般式（Ｊ－３）中、Ｒ^２は、エーテル結合含有脂肪族化合物（Ｄ）由来の基を表し、Ｑ^２は、２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、ｚ^１は、１以上の平均繰り返し数であり、ｘ^１は、０．１以上の平均繰り返し数を表す。）

（上記一般式（Ｊ－４）中、Ａｒ^２は、芳香族モノアルコール（Ｂ）由来の基を表す。）

（上記一般式（Ｊ－５）中、Ｑ^１は、２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、Ａｒ^１は、芳香族モノアルコール（Ｂ）由来の基を表す。）
（本明細書における＊は他の原子との結合手を表す。但し、酸素原子が隣接（－Ｏ－Ｏ－）して結合することはない。）
上記一般式（Ｊ－１）で表されるように、リン含有多価アルコール化合物（Ｃ）由来の基であるＡは、２価～４価の基であることが好ましく、２価又は３価の基であることがより好ましい。
なお、上記一般式（Ｊ－１）～（Ｊ－５）中の各由来の基は、説明の便宜上、一般式（Ｊ）中の記号と各原料成分との対応関係を表す用語であって、反応によってリン含有活性エステル内に残る各反応原料由来の構造部位を全て表すものではない。
これにより、得られる硬化物において、伸度、密着性及び低誘電特性をよりバランスよく向上させることができる。 The phosphorus-containing active ester of the present embodiment includes a partial structure represented by the following general formula (J-1), a divalent partial structure represented by the following general formula (J-2), and the following general formula (J -3), a monovalent partial structure represented by the following general formula (J-4), and a monovalent partial structure represented by the following general formula (J-5) and preferably. A more preferred form of the phosphorus-containing active ester is a partial structure represented by the following general formula (J-1), a divalent partial structure represented by the following general formula (J-2) and the following general formula (J-3 ), and the following general formula (J-4) and/or the following general formula ( It has a partial structure represented by J-5).

(In the above general formula (J-1), A represents a divalent to tetravalent group derived from the phosphorus-containing polyhydric alcohol compound (C), and each dashed line is independently absent or a single bond. .)

(In general formula (J-2) above, R ¹ represents a group derived from an ether bond-containing aliphatic compound (D), and y ¹ represents an average number of repetitions of 1 or more.)

(In general formula (J-3) above, R ² represents a group derived from an ether bond-containing aliphatic compound (D), and Q ² represents an aromatic compound having two or more carboxyl groups and/or an acid halogen thereof. represents a group derived from compound or ester compound (A), z ¹ represents an average number of repetitions of 1 or more, and x ¹ represents an average number of repetitions of 0.1 or more.)

(In general formula (J-4) above, Ar ² represents a group derived from the aromatic monoalcohol (B).)

(In general formula (J-5) above, Q ¹ represents an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A)-derived group, and Ar ¹ is an aromatic represents a group derived from monoalcohol (B).)
(* in this specification represents a bond with another atom. However, oxygen atoms are not adjacent (-O-O-) and bonded.)
As represented by the above general formula (J-1), A, which is a group derived from the phosphorus-containing polyhydric alcohol compound (C), is preferably a divalent to tetravalent group, and is divalent or trivalent. is more preferably a group of
For convenience of explanation, the groups derived from each of the general formulas (J-1) to (J-5) are terms that represent the correspondence between the symbols in the general formula (J) and each raw material component. , do not represent all the structural sites derived from each reactant that remain in the phosphorus-containing active ester after the reaction.
Thereby, elongation, adhesion and low dielectric properties can be improved in a well-balanced manner in the obtained cured product.

A in the above general formula (J-1) is a group derived from the phosphorus-containing polyhydric alcohol compound (C), and is a hydrocarbon bond (divalent to hexavalent hydrocarbon group), carbonate bond, ester bond, It may contain at least one bond structure selected from the group consisting of an ether bond, a urethane bond, and a siloxane bond. In addition, each dashed line in general formula (J-1) above may be absent or a single bond. Therefore, when both of the dashed lines are absent, A represents a divalent group, and when one of the two dashed lines is absent, A represents a trivalent group, and the two dashed lines When both are single bonds, A represents a tetravalent group.
The group derived from the phosphorus-containing polyhydric alcohol compound (C) preferably has 1 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and 6 to 25 carbon atoms. is more preferred.

Phosphorus in the group derived from the phosphorus-containing polyhydric alcohol compound (C) is not particularly limited such as the valence of the phosphorus (-3, -1, +1, +3, +5) and the bonding form of phosphorus, For example, it preferably exists in the form of pentavalent phosphorus in which an oxo group (=O) is directly bonded to a phosphorus atom, that is, as an oxoline (V) group (≡P(=O)). Therefore, the group derived from the phosphorus-containing polyhydric alcohol compound (C) preferably has an oxoline (V) group (≡P(=O)), and the phosphorus of the oxoline (V) group (≡P(=O)) More preferably, the atom has three hydrocarbon groups attached directly or through an oxygen (--O--).
In addition, the group derived from the phosphorus-containing polyhydric alcohol compound (C) includes a group containing phosphorus and a divalent or higher aliphatic hydrocarbon group or a divalent or higher cyclic hydrocarbon group. more preferably an aromatic group containing an oxoline (V) group (≡P(=O)). More specifically, the group derived from the phosphorus-containing polyhydric alcohol compound (C) includes a phosphorus or oxoline (V) group (≡P(=O)) and a linear or branched alkylene group , a linear or branched alkylene ether group, or a hydrocarbon group having an aromatic ring (arylene group or aralkylene group), and a hydrocarbon group having the alkylene group, alkylene ether group or aromatic ring —CH ₂ — in may be substituted with —O— or —S— so that they are not adjacent to each other, or one or more —CH ₂ —CH ₂ — in the alkylene group are not adjacent to each other, It may be substituted with at least one selected from the group consisting of -CH=CH-, a carbonate bond, an ester bond, an ether bond, a urethane bond and a siloxane bond.

As a preferred form of the group derived from the phosphorus-containing polyhydric alcohol compound (C), an oxoline (V) group (≡P(=O)) and a carbonized group bonded to the oxoline(V) group (≡P(=O)) A group having a hydrogen group is preferable, and an oxoline (V) group (≡P(=O)) and a cyclic group of 2 or more and 7 or less bonded to the oxoline(V) group (≡P(=O)) A group having (for example, an aromatic ring) is more preferable.
When the cyclic group in the group derived from the phosphorus-containing polyhydric alcohol compound (C) is a condensed polycyclic hydrocarbon, one assembly of the cyclic group is counted as one. Thus, for example, when the fused polycyclic hydrocarbon is a phenanthrene group, the number of cyclic groups is one.
A hydrocarbon in which two or more ring systems are directly linked by a single or double bond and the number of such bonds is one less than the number of ring systems is called a ring-assembled hydrocarbon. Each ring system is counted as one when the group derived from the phosphorus-containing polyhydric alcohol compound (C) has such a ring-assembled hydrocarbon. For example, when the ring-assembled hydrocarbon is a terphenyl group, the number of cyclic groups is three.

［上記一般式（ｊ）中、Ｍ^ｊは（ｎ^１＋１）価の芳香族基を表し、Ｒ^３及びＲ^４はそれぞれ独立して、一価の炭化水素基又は二価の炭化水素基を表し、Ｒ^３又はＲ^４の一方が二価の炭化水素基である場合、他方も二価の炭化水素基であり、かつＲ^３及びＲ^４が互いに結合した環状構造を形成し、ｎ^１は２～４の整数を表し、上記一般式（ｊ）中の＊は、酸素原子と結合する結合手を表す。］を表すことが好ましい。また、上記一般式（ｊ）の破線部はＲ^３及びＲ^４が互いに結合する場合があることを示している。 A in the above general formula (J-1) is represented by the following general formula (j):

[In the above general formula (j), M ^j represents a (n ¹ +1)-valent aromatic group, and R ³ and R ⁴ each independently represent a monovalent hydrocarbon group or a divalent hydrocarbon group. When one of R ³ or R ⁴ is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R ³ and R ⁴ are bonded together to form a cyclic structure, and n ¹ is It represents an integer of 2 to 4, and * in the above general formula (j) represents a bond that bonds with an oxygen atom. ] is preferred. Also, the dashed line in the general formula (j) indicates that R ³ and R ⁴ may bond with each other.

In the general formula (j), ⁿ¹ preferably represents an integer of 2 or more and 4 or less, more preferably 2 or 3. When ⁿ¹ is 3, for example, ^Mj is a tetravalent group, and means that there are three bonds that bond to an oxygen atom.
In the above general formula (j), M ^j is an (n ¹ +1) valent aromatic group, and (n ¹ +1) hydrogen atoms from a monocyclic aromatic ring, condensed aromatic ring or ring assembly aromatic ring Groups without atoms are included. For example ^Mj is benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, one aromatic group selected from the group consisting of phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene and quaterphenyl and a group obtained by removing (n ¹ +1) hydrogen atoms from the one aromatic group. In addition, the one aromatic group may be unsubstituted, or the hydrogen atom of the aromatic ring in the aromatic group is, for example, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. It may be substituted with up to 10 alkoxy groups or halogen atoms.

In the above general formula (j), the monovalent hydrocarbon group preferably includes a linear, branched or cyclic saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic group, such as an alkyl group, an alkenyl one group selected from the group consisting of groups, aryl groups, aralkyl groups and alkoxy groups, wherein any one or more —CH ₂ — in the selected one group are not adjacent to each other, More preferably, it may be substituted with -O- or -S-. Further, the monovalent hydrocarbon group preferably has 1 to 20 carbon atoms.
In the general formula (j), the divalent hydrocarbon group preferably includes a linear, branched or cyclic saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic group, such as an alkylene group, an alkenylene a group selected from the group consisting of an arylene group, an aralkylene group and an alkylene ether group, wherein any one or more —CH ₂ — in the selected one group are not adjacent to each other. , —O— or —S— is more preferred. Further, the divalent hydrocarbon group preferably has 1 to 20 carbon atoms.

R ¹ in general formula (J-2) above preferably represents a group derived from the ether bond-containing aliphatic compound (D). R ² in general formula (J-3) above preferably represents a group derived from the ether bond-containing aliphatic compound (D). Moreover, it is preferable that R ¹ and R ² in the general formulas (J-2) and (J-3) each independently represent a group derived from the ether bond-containing aliphatic compound (D). Also, R ¹ and R ² may be the same as each other or different from each other. For example, preferred forms of R ¹ and R 2 in general formulas (J-2) and (J- ³ ) above are preferred forms of R 1 and R ² in general formulas (J) and general formula ( ¹ ) below. is similar to
Q ² in general formula (J-3) above preferably represents a group derived from an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A). Q ¹ in general formula (J-5) above preferably represents a group derived from an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (A). In addition, Q ¹ and Q ² in the general formulas (J-3) and (J-5) are each independently, and Q ¹ and Q ² may be the same or different from each other. may For example, preferred forms of Q ¹ and Q 2 in general formula (J-3) and general formula (J-5) above are Q ^{1 and Q 2 in} general formula (J) and general formula ( ¹ ) below. Similar to the preferred form.

Ar ² in general formula (J-4) above preferably represents a group derived from the aromatic monoalcohol (B). Ar ¹ in general formula (J-5) above preferably represents a group derived from the aromatic monoalcohol (B). Ar ¹ and Ar ² in the general formulas (J-4) and (J-5) are each independently, for example, preferably a substituted or unsubstituted aromatic group, a substituted or unsubstituted aryl group or Aralkyl groups are more preferred. In general formulas (J-4) and (J-5) above, Ar ¹ and Ar ² may be the same as or different from each other. For example, preferred forms of Ar ¹ and Ar ² in general formulas (J-4) and (J-5) above may be general formulas (2) or (3) described below, and further, Preferred forms of Ar ¹ and Ar ² in general formulas (J-4) and (J-5) above are the same as the preferred forms of Ar ¹ and Ar ² in general formula (1) below.

y ¹ in the general formula (J-2) is preferably an average repetition number of 1 or more, and among them, from the viewpoint of workability and flexibility of the resulting cured product, the average repetition number y ¹ is 1 ~5 is more preferred.
z ¹ in the general formula (J-3) is preferably an average repetition number of 1 or more, and among them, from the viewpoint of workability and flexibility of the resulting cured product, the average repetition number z ¹ is 1 ~5 is more preferred.
The average number of repetitions x ¹ , y ¹ and z ¹ of the phosphorus-containing active ester can be calculated from the charge ratio or NMR, etc., as shown in the Examples section below.

A more preferable form of the phosphorus-containing active ester of the present embodiment is a divalent to tetravalent partial structure represented by the general formula (J-1) and 2 to 4 represented by the general formula (J-1). Consists of a divalent partial structure represented by general formula (J-2) and a divalent partial structure represented by general formula (J-3) chemically bonded to a valent partial structure. It has a repeating unit and a partial structure represented by the general formula (J-4) and/or the general formula (J-5) chemically bonded to the repeating unit as a terminal part of the repeating unit, The repeating number x ¹ of the repeating unit is preferably the average repeating number, preferably 0.1 or more. An average number of repetitions of 3 is more preferred, and an average number of repetitions of 0.7 to 2.8 is even more preferred.
Further, for the divalent partial structure represented by the general formula (J-1), the divalent partial structure represented by the general formula (J-2) and the general formula (J-3) It is preferred that the represented divalent partial structures are chemically bonded to form a repeating unit. Furthermore, with respect to the trivalent partial structure represented by the general formula (J-1), the divalent partial structure represented by the general formula (J-2) is 1 or 2, and the general formula It is preferable that the divalent partial structure 2 or 1 represented by (J-3) is chemically bonded to form a repeating unit. Then, with respect to the tetravalent partial structure represented by the general formula (J-1), there are 1 to 3 divalent partial structures represented by the general formula (J-2), and the general formula Preferably, 3 to 1 divalent partial structures represented by (J-3) are chemically bonded to form a repeating unit.

（上記一般式（Ｊ）中、Ａは、前記リン含有多価アルコール化合物（Ｃ）由来の基を表し、Ｒ^１及びＲ^２はそれぞれ独立して、前記エーテル結合含有脂肪族化合物（Ｄ）由来の基を表し、Ｑ^１及びＱ^２は、前記２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、Ａｒ^１及びＡｒ^２はそれぞれ独立して、前記芳香族モノアルコール（Ｂ）由来の基を表し、Ｍ^ａは、下記一般式（ｉｉ）又は（ｉｉｉ）で表される基を表し、

［上記一般式（ｉｉ）又は（ｉｉｉ）中、Ｒ^３はそれぞれ独立して、前記エーテル結合含有脂肪族化合物（Ｄ）由来の基を表し、Ｑ^３及びＱ^４はそれぞれ独立して、前記２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、Ａｒ^３及びＡｒ^４はそれぞれ独立して、前記芳香族モノアルコール（Ｂ）由来の基を表し、ｘ^２は、０．１以上の平均繰り返し数であり、ｙ^２は、１以上の平均繰り返し数である。］
ｘ^１は、０．１以上の平均繰り返し数であり、ｙ^１は、１以上の平均繰り返し数であり、ｚ^１は、１以上の平均繰り返し数であり、ｑは０又は１を表す。）で表される化合物でありうる。なお、ｑが０のときは、Ａは２つの結合手（二価）を有し、ｑが１のときは、Ａは３つの結合手（三価）を有する。
これにより、得られる硬化物において、伸度、密着性及び低誘電特性をよりバランスよく向上させることができる。 The phosphorus-containing active ester of this embodiment is preferably represented by the following general formula (J).

(In the above general formula (J), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and R ¹ and R ² are each independently derived from the ether bond-containing aliphatic compound (D) and Q ¹ and Q ² represent groups derived from the aromatic compound having two or more carboxyl groups and/or acid halides or esters thereof (A), and Ar ¹ and Ar ² are each independently represents a group derived from the aromatic monoalcohol (B), ^Ma represents a group represented by the following general formula (ii) or (iii),

[In the above general formula (ii) or (iii), R ³ each independently represents a group derived from the ether bond-containing aliphatic compound (D), and Q ³ and Q ⁴ each independently represent the 2 Represents a group derived from an aromatic compound having a carboxyl group and / or an acid halide or ester thereof (A), and Ar ³ and Ar ⁴ are each independently a group derived from the aromatic monoalcohol (B) where ^x2 is an average repetition number of 0.1 or more, and ^y2 is an average repetition number of 1 or more. ]
^x1 is an average repetition number of 0.1 or more, ^y1 is an average repetition number of 1 or more, ^z1 is an average repetition number of 1 or more, and q represents 0 or 1. ) can be a compound represented by When q is 0, A has two bonds (divalent), and when q is 1, A has three bonds (trivalent).
Thereby, elongation, adhesion and low dielectric properties can be improved in a well-balanced manner in the obtained cured product.

［上記一般式（Ｉ）中、Ｍ^１は芳香族基を表し、Ｒ^３及びＲ^４はそれぞれ独立して、一価の炭化水素基又は二価の炭化水素基を表し、Ｒ^３又はＲ^４の一方が二価の炭化水素基である場合、他方も二価の炭化水素基であり、かつＲ^３及びＲ^４が互いに結合した環状構造を形成し、上記一般式（Ｉ）中の＊は、酸素原子と結合する結合手を表す。］を表すことが好ましい。また、上記一般式（Ｉ）の破線部はＲ^３及びＲ^４が互いに結合する場合があることを示している。 In the above general formula (J), A is the following general formula (I):

[In general formula (I) above, M ¹ represents an aromatic group, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group or a divalent hydrocarbon group, and R ³ or R ⁴ is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R ³ and R ⁴ are bonded together to form a cyclic structure, and * in the general formula (I) is , represents a bond that bonds with an oxygen atom. ] is preferably represented. Also, the dashed line in the above general formula (I) indicates that R ³ and R ⁴ may bond with each other.

In the above general formula (I), M ^j is an (n ¹ +1) valent aromatic group, and (n ¹ +1) hydrogen atoms from a monocyclic aromatic ring, condensed aromatic ring or ring assembly aromatic ring Groups without atoms are included. For example M ^j is benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, one aromatic group selected from the group consisting of phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene and quaterphenyl and a group obtained by removing (n ¹ +1) hydrogen atoms from the one aromatic group.
Moreover, the preferred form of the above general formula (I) or the preferred form of R ³ and R ⁴ in the above general formula (I) are the same as those of the above general formula (j).

（上記一般式（Ｉ－１）～（Ｉ－１２）中、Ｒ^３及びＲ^４はそれぞれ独立して、アルキル基、アルコキシ基、アリル基、アリール基、アリールオキシ基、アラルキル基、又はナフチル基を表し、Ｒ^５はそれぞれ独立して、アルキル基又はアルコキシ基を表し、ｎ^ｉ１は０～３の整数を表し、ｎ^ｉ３は０～６の整数を表し、ｎ^ｉ２、ｎ^ｉ４、ｎ^ｉ５及びｎ^ｉ６は０～５の整数を表す。）また、上記一般式（Ｉ－１）～（Ｉ－６）で表される基は、Ａが二価の基である。一方上記一般式（Ｉ－７）～（Ｉ－１２）で表される基は、Ａが三価の基であり、３つめの結合手は芳香族環のいずれかに存在しうる。 In A in the general formula (J), when R ³ and R ⁴ are each independently a monovalent hydrocarbon group, an aromatic group having 3 to 30 carbon atoms is preferable, and 6 to 6 carbon atoms. 24 aromatic groups are more preferred. When R ³ and R ⁴ are each independently a monovalent hydrocarbon group, a particularly preferred form of A is any group represented by the following general formulas (I-1) to (I-12). mentioned.

(In general formulas (I-1) to (I-12) above, R ³ and R ⁴ are each independently an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or a naphthyl group. , each R ⁵ independently represents an alkyl group or an alkoxy group, n ⁱ¹ represents an integer of 0 to 3, n ⁱ³ represents an integer of 0 to 6, n ⁱ² , n ⁱ⁴ , n ⁱ⁵ and n ⁱ⁶ represents an integer of 0 to 5.) In the groups represented by the general formulas (I-1) to (I-6), A is a divalent group. On the other hand, in the groups represented by the above general formulas (I-7) to (I-12), A is a trivalent group, and the third bond can exist in any of the aromatic rings.

（上記一般式（Ｉ－２１）～（Ｉ－２８）中、Ｒ^５及びＲ^６はそれぞれ独立して、アルキル基又はアルコキシ基を表し、ｎ^ｉＩ７～ｎ^ｉＩ１４は０～８の整数を表し、ｎ^ｉ８、ｎ^ｉ１０～ｎ^ｉ１２は０～５の整数を表し、ｎ^ｉ９は０～７の整数を表し、ｎ^ｉ７、ｎ^ｉ１３及びｎ^ｉ１４は０～３の整数を表す。なお、Ｒ^５は芳香族基を表すＭ^１全体の置換基を表し、Ｒ^６はＲ^３及びＲ^４が互いに結合した環状構造全体の置換基を表す。）また、上記一般式（Ｉ－１３）～（Ｉ－２０）で表される基は、Ａが二価の基である。一方、上記一般式（Ｉ－２１）～（Ｉ－２８）で表される基は、Ａが三価の基であり、３つめの結合手は芳香族環のいずれかに存在しうる。 In A in the general formula (1), when R ³ and R ⁴ are each independently a divalent hydrocarbon group, an alkyl group, an alkoxy group, an allyl group or an aryl group is preferable.
When R ³ and R ⁴ are each independently a divalent hydrocarbon group, a particularly preferred form of A is any one of the following general formulas (I-13) to (I-20). mentioned.

(In general formulas (I-21) to (I-28) above, R ⁵ and R ⁶ each independently represent an alkyl group or an alkoxy group, n ^iI7 to n ^iI14 represent an integer of 0 to 8, n ⁱ⁸ , n ⁱ¹⁰ to n ⁱ¹² represent an integer of 0 to 5, n ⁱ⁹ represents an integer of 0 to 7, n ⁱ⁷ , n ⁱ¹³ and n ⁱ¹⁴ represent an integer of 0 to 3. R ⁵ is Represents a substituent for the entire M ¹ representing an aromatic group, and R ⁶ represents a substituent for the entire cyclic structure in which R ³ and R ⁴ are bonded to each other.) In addition, general formulas (I-13) to (I- In the group represented by 20), A is a divalent group. On the other hand, in the groups represented by the general formulas (I-21) to (I-28), A is a trivalent group, and the third bond can exist in any of the aromatic rings.

A in the general formula (J) preferably has a cyclic group, more preferably an aromatic group. As a result, the structure of A contains a phosphorus atom and has a high concentration of aromatic rings, so that it can contribute to the effect of improving the flame retardancy based on the phosphorus-containing active ester, which is preferable. Known active esters having an aliphatic cyclic hydrocarbon group in the molecular structure are excellent in dielectric properties (low dielectric properties) in the resulting cured product, but are easily flammable and have insufficient heat resistance. However, by introducing a plurality of aromatic rings into the molecular structure of the phosphorus-containing active ester of the present embodiment, elongation, adhesion and dielectric properties can be combined at a higher level. In addition, the phosphorus-containing active ester having a bulky substituent structure, such as the structure represented by the general formula (I), has a higher activity to participate in the curing reaction than an active ester having no bulky substituent structure. Since the group concentration is lowered, the heat resistance of the cured product tends to be poor. As a result, the phosphorus-containing active ester of the present disclosure is characterized not only by elongation, adhesion, and dielectric properties, but also by excellent flame retardancy or heat resistance, and can combine various performances.

R ¹ , R ² , R ⁱⁱ and R ⁱⁱⁱ in the general formula (J), general formula (ii) and general formula (iii) each independently represent a group derived from the ether bond-containing aliphatic compound (D) It is preferable to express In addition, R ¹ , R ² , R ⁱⁱ and R ⁱⁱⁱ may be the same as or different from each other. For example, each of R ¹ , R ² , R ⁱⁱ and R ⁱⁱⁱ in general formula (J-1) above preferably independently represents a group derived from the ether bond-containing aliphatic compound (D). For example, the group derived from the ether bond-containing aliphatic compound (D) is preferably a linear, branched or cyclic divalent hydrocarbon group, and a linear or branched alkylene group. is more preferred. The number of carbon atoms in the linear or branched alkylene group is more preferably 2-16, and even more preferably 2-10. When the number of carbon atoms is within the above range, the phosphorus-containing active ester has excellent compatibility, which is a preferred embodiment.

Q ¹ , Q ² , Q ³ and Q ⁴ in general formula (J), general formula (ii) and general formula (iii) are each independently an aromatic compound having two or more carboxyl groups and/or It preferably represents a group derived from its acid halide or ester (A). Also, ^Q1 , ^Q2 , ^Q3 and ^Q4 may be the same or different. For example, preferred forms of each of Q ¹ , Q ² , Q ³ and Q ⁴ in general formula (J) are, for example, groups derived from aromatic polycarboxylic acids (A), such as divalent aromatic is preferably a group, more preferably an unsubstituted divalent aromatic group. Q ¹ , Q ² , Q ³ and Q ⁴ in general formula (J), general formula (ii) and general formula (iii) are preferably divalent aromatic groups. Examples of the divalent aromatic group include groups obtained by removing two hydrogen atoms from the above examples of aromatic rings having 3 to 30 carbon atoms. Among them, Q ¹ , Q ² , Q ³ and Q ⁴ are more preferably phenylene group, naphthalenediyl group or anthracenediyl group. These phenylene groups, naphthalenediyl groups, or anthracenediyl groups may be unsubstituted, or alternatively, halogen atoms, cyano groups, amino groups, alkyl groups having 1 to 10 carbon atoms, or It may be substituted with an alkoxy group. Among them, Q ¹ , Q ² , Q ³ and Q ⁴ are more preferably unsubstituted phenylene groups from the viewpoint of industrial availability of raw materials and solubility.

［上記一般式（２）及び一般式（３）中の＊は、上記一般式（１）中のＡｒ^１、Ａｒ^２と結合する酸素原子との結合手を表し、
Ｒ^２１及びＲ^３１はそれぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリール基又はアラルキル基を表し、ｋ^２１は、０～７の整数を表し、及びｋ^３１は、０～５の整数を表す。］で表されることが好ましい。 Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the general formula (J), general formula (ii) and general formula (iii) each independently represent a group derived from the aromatic monoalcohol (B). is preferred. For example, a substituted or unsubstituted aromatic group is preferred, and a substituted or unsubstituted aryl group or aralkyl group is more preferred. In general formula (J), general formula (ii) and general formula (iii), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may be the same or different.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the general formula (J), general formula (ii) and general formula (iii) are each independently, for example, as a group derived from the aromatic monoalcohol (B) , the following general formula (2) or (3):

[* in the above general formulas (2) and (3) represents a bond with the oxygen atom that binds to Ar ¹ and Ar ² in the above general formula (1),
R ²¹ and R ³¹ each independently represent a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aralkyl group, k ²¹ represents an integer of 0 to 7, and k ³¹ represents 0 to Represents an integer of 5. ] is preferably represented.

In general formula (J) and general formula (ii) above, Ar ¹ and Ar ³ are each independently preferably a group having a structure represented by general formula (3) above. In general formula (J) and general formula (iii) above, Ar ² and Ar ⁴ are each independently preferably a group having a structure represented by general formula (3) above.

R ²¹ in the general formula (2) is preferably a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aralkyl group. from the viewpoint of flexibility, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, an aralkyl group such as a diphenylmethyl group or a naphthylmethyl group, or a phenyl group, a naphthyl group, An arylene group such as a phenalenyl group, a phenanthrenyl group or an anthryl group is more preferred.
R ³¹ in the general formula (3) is preferably a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aralkyl group. from the viewpoint of flexibility, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, an aralkyl group such as a diphenylmethyl group or a naphthylmethyl group, or a phenyl group, a naphthyl group, An arylene group such as a phenalenyl group, a phenanthrenyl group or an anthryl group is more preferred.
k ²¹ in the general formula (2) is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and from the viewpoint of reactivity or flexibility of the resulting cured product, 0 More preferably, it is an integer of ~4. Further, k ³¹ in the general formula (3) is preferably an integer of 0 to 5, and more preferably an integer of 0 to 4 from the viewpoint of reactivity or flexibility of the resulting cured product. .

x ¹ in the general formula (J) is preferably an average repetition number of 0.1 or more, and among them, an average repetition number of 0.5 to 3 from the viewpoint of workability and flexibility of the resulting cured product number, and more preferably an average repetition number of 0.7 to 2.8. In addition, x ² in the general formula (J) is preferably an average repetition number of 0.1 or more, and among them, from the viewpoint of workability and flexibility of the resulting cured product, 0.5 to 3 More preferably, the average number of repetitions is 0.7 to 2.8.
y ¹ in the general formula (J) preferably has an average repetition number of 1 or more, and more preferably 1 to 5 from the viewpoint of workability and flexibility of the resulting cured product. In addition, y ² in the general formula (J) is preferably an average repetition number of 1 or more, and more preferably 1 to 5 from the viewpoint of workability and flexibility of the resulting cured product. preferable.
z ¹ in the general formula (J) is preferably an average number of repetitions of 1 or more. Among them, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions z ¹ is 1 to 5. is more preferable.

［上記一般式（１）中、Ａは、前記リン含有多価アルコール化合物（Ｃ）由来の基を表し、Ｒ^１及びＲ^２はそれぞれ独立して、前記エーテル結合含有脂肪族化合物（Ｄ）由来の基を表し、Ｑ^１及びＱ^２は、前記２以上のカルボキシル基を有する芳香族化合物及び／又はその酸ハロゲン化物若しくはエステル化物（Ａ）由来の基を表し、Ａｒ^１及びＡｒ^２はそれぞれ独立して、前記芳香族モノアルコール（Ｂ）由来の基を表し、ｘ^１は、０．１以上の平均繰り返し数であり、ｙ^１は、１以上の平均繰り返し数であり、ｚ^１は、１以上の平均繰り返し数である。］で表される化合物でありうる。
なお、上記各由来の基は、説明の便宜上、一般式（１）中の記号と各原料成分との対応関係を表す用語であって、反応によってリン含有活性エステル内に残る各反応原料由来の構造部位を全て表すものではない。
これにより、難燃性を示し、かつ得られる硬化物において、伸度、密着性及び低誘電特性をよりバランスよく向上させることができる。 The phosphorus-containing active ester of this embodiment can be a compound represented by the following general formula (1). In other words, a preferred form of the phosphorus-containing active ester represented by the general formula (J) is represented by the following general formula (1).

[In the above general formula (1), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and R ¹ and R ² are each independently derived from the ether bond-containing aliphatic compound (D) and Q ¹ and Q ² represent groups derived from the aromatic compound having two or more carboxyl groups and/or acid halides or esters thereof (A), and Ar ¹ and Ar ² are each independently represents a group derived from the aromatic monoalcohol (B), x ¹ is an average repetition number of 0.1 or more, y ¹ is an average repetition number of 1 or more, z ¹ is 1 It is the above average number of repetitions. ] can be a compound represented by
In addition, for convenience of explanation, the groups derived from each of the above are terms that represent the correspondence between the symbols in the general formula (1) and each raw material component. Not all structural sites are represented.
Thereby, it is possible to improve elongation, adhesion and low dielectric properties in a well-balanced manner in the resulting cured product which exhibits flame retardancy.

In general formula (1) above, preferred forms of A are the same as in general formula (J) above. Therefore, A in the general formula (1) preferably has a cyclic group, and more preferably has an aromatic group. As a result, the structure of A contains a phosphorus atom and has a high concentration of aromatic rings, so that it can contribute to the effect of improving the flame retardancy based on the phosphorus-containing active ester, which is more preferable. Known active esters having an aliphatic cyclic hydrocarbon group in the molecular structure are excellent in dielectric properties (low dielectric properties) in the resulting cured product, but are easily flammable and have insufficient heat resistance. However, by introducing a plurality of aromatic rings into the molecular structure of the phosphorus-containing active ester of the present embodiment, not only dielectric properties, elongation and adhesion, but also flame retardancy can be achieved at a high level. . In addition, the phosphorus-containing active ester having a bulky substituent structure, such as the structure represented by the general formula (I), has a higher activity to participate in the curing reaction than an active ester having no bulky substituent structure. Since the group concentration is lowered, the heat resistance of the cured product tends to be poor. As a result, the phosphorus-containing active ester of the present disclosure has not only excellent dielectric properties, elongation, and adhesion, but also excellent flame retardancy and heat resistance, and can have various performances.

Preferred forms of R ¹ and R ² in general formula (1) above are the same as the preferred forms of R ¹ and R ² in general formula (1) above. R ¹ and R ² in the general formula (1) are more preferably linear or branched alkylene groups. The number of carbon atoms in the linear or branched alkylene group is more preferably 2-16, and even more preferably 2-10. When the number of carbon atoms is within the above range, the phosphorus-containing active ester has excellent compatibility, which is a preferred embodiment.

Q ¹ or Q ² in general formula (1) above is the same as the preferred form of Q ¹ or Q ² in general formula (J) above. Also, Q ¹ and Q ² may be the same as or different from each other.

［上記一般式（２）及び一般式（３）中の＊は、上記一般式（１）中のＡｒ^１又はＡｒ^２と結合する酸素原子との結合手を表し、
Ｒ^２１及びＲ^３１はそれぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリール基又はアラルキル基を表し、ｋ^２１は、０～７の整数を表し、及びｋ^３１は、０～５の整数を表す。］で表されることが好ましい。 Ar ¹ and Ar ² in the above general formula (1) are represented by the following general formula (2) or (3):

[* in the above general formulas (2) and (3) represents a bond with the oxygen atom that binds to Ar ¹ or Ar ² in the above general formula (1),
R ²¹ and R ³¹ each independently represent a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aralkyl group, k ²¹ represents an integer of 0 to 7, and k ³¹ represents 0 to Represents an integer of 5. ] is preferably represented.

In the above general formula (1), Ar ¹ and Ar ² may be the same as or different from each other.
In general formula (1) above, Ar ¹ is preferably a group having a structure represented by general formula (3) above. In general formula (1) above, Ar ² is preferably a group having a structure represented by general formula (3) above.
A preferred form of Ar ¹ and Ar ² in the general formula (1) may be the general formula (2) or (3), and further Ar ¹ or Ar ² in the general formula (J) may be similar to the preferred form of

x ¹ in the general formula (1) is preferably an average repetition number of 0.1 or more, and among them, an average repetition number of 0.5 to 3 from the viewpoint of workability and flexibility of the resulting cured product number, and more preferably an average repetition number of 0.7 to 2.8.
The average repetition number ^x1 of the phosphorus-containing active ester can be calculated from the charge ratio, NMR, or the like. For example, when calculating from the preparation ratio, it is calculated by the following formula (1).
Formula (1): (average number of repetitions x ¹ in the obtained phosphorus-containing active ester) = (reactant (E) of phosphorus-containing polyhydric alcohol compound (C) and ether bond-containing aliphatic compound (D) number of moles of hydroxyl groups) / [(number of moles of active ester groups in the active ester group-containing intermediate product (a ') generated from the reaction raw material) - (phosphorus-containing polyhydric alcohol compound (C) and ether bond-containing Number of moles of hydroxyl groups in the reactant (E) with the aliphatic compound (D))]
The active ester group-containing intermediate (a') is an aromatic polycarboxylic acid, its acid halide and/or esterified product (A), and an aromatic monoalcohol (B) as reaction raw materials. is a reaction product.

y ¹ in the above general formula (1) is preferably an average number of repetitions of 1 or more. Among them, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions y ¹ is 1 to 5. is more preferable.
z ¹ in the general formula (1) is preferably an average number of repetitions of 1 or more. Among them, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions z ¹ is 1 to 5. is more preferable.
The average number of repetitions ^y1 and ^z1 of the phosphorus-containing active ester can be calculated from the charge ratio or NMR, etc., as shown in the Examples section below.

<Reactive raw material for phosphorus-containing active ester>
Aromatic polycarboxylic acids (A) (compounds having a partial structure represented by Q ¹ and / or Q ² in the above general formula (1)) and aromatic monoalcohols (B)) (the above general formula (1 ) and a compound having a partial structure represented by Ar ¹ and / or Ar ² of ) and a phosphorus-containing polyhydric alcohol compound (C) (a compound having a partial structure represented by A in the general formula (1)) , an ether bond-containing aliphatic compound (D) (a compound having a partial structure represented by R ¹ and / or R ² in the general formula (1)) is used as a reaction raw material to obtain a phosphorus-containing active ester. .
Then, in the structure of the phosphorus-containing active ester, a structural site exhibiting flame retardancy derived from the phosphorus-containing polyhydric alcohol compound (C) (for example, A in the general formula (1)) and a terminal having high curability An ester group (specifically, a polyaryloxycarbonyl structure) having an aromatic ring (e.g., Q ¹ and/or Q ² and Ar ¹ and/or Ar ² in the general formula (1)), and a flexible segment and an alkylene ether group (for example, (R ¹ O) or (R ² O) in the above general formula (1)) can form an ester compound having high reaction activity.
The reaction raw materials for the phosphorus-containing active ester are described below.
-Aromatic compounds having two or more carboxyl groups and/or acid halides or esters thereof (A)-
In the present embodiment, an aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof (A) (the partial structure represented by Q1 and/or ^Q2 in the above general formula ( ¹ ) compound) is a carboxylic acid having two or more carboxyl groups, or a derivative thereof, specifically a carboxylic oxide, acid halide or ester.

Aromatic polycarboxylic acids (A) are typically compounds in which at least two carboxyl groups or the like are bonded to a substituted or unsubstituted aromatic ring. However, the portion such as the carboxyl group, other than the carboxyl group, acyl halide group such as acyl fluoride group, acyl chloride group, acyl bromide group; alkyloxycarbonyl group such as methyloxycarbonyl group, ethyloxycarbonyl group an aryloxycarbonyl group such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group; That is, when the portion such as the carboxyl group is a halogenated acyl group, the aromatic polycarboxylic acids (A) are acid halides. Similarly, when the portion such as the carboxyl group is an alkyloxycarbonyl group or an aryloxycarbonyl group, the aromatic polycarboxylic acids (A) are esterified products. The aromatic polycarboxylic acids (A) preferably have a carboxyl group, a halogenated acyl group, and an aryloxycarbonyl group, and more preferably have a carboxyl group and a halogenated acyl group, and a carboxyl group and an acyl chloride. It is more preferred to have an acyl bromide group.
The aromatic ring is not particularly limited, but includes a monocyclic aromatic ring, a condensed ring aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by an alkylene chain. The aromatic ring is preferably a monocyclic aromatic ring or a condensed aromatic ring from the viewpoints of the flexibility of the resulting cured product, the ease of industrial availability of raw materials, and workability.

The valence (number) of the carboxyl groups in the aromatic polycarboxylic acids (A) is preferably bivalent to tetravalent, more preferably bivalent.

Specific examples of aromatic polycarboxylic acids (A) include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid; trimellitic acid, 5-allyl trimellitic acid, and the like. benzenetricarboxylic acid; naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalenedicarboxylic acids such as 3-allylnaphthalene-1,4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof.

Among the above-mentioned examples, the aromatic polycarboxylic acids (A) include benzenedicarboxylic acid, benzenetricarboxylic acid, and naphthalene from the viewpoint of the flexibility of the resulting cured product, the ease of industrial availability of raw materials, and workability. Dicarboxylic acids, preferably acid halides thereof, isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2 ,7-dicarboxylic acid and 1,3,5-benzenetricarboxylic acid. Acid halides thereof are more preferred, and isophthalic acid chloride and terephthalic acid chloride are more preferred.
The aromatic polycarboxylic acids (A) may be used singly or in combination of two or more.

-Aromatic monoalcohol (B)-
Aromatic monoalcohol (B) is an aromatic compound having an aromatic ring and one phenolic hydroxyl group. Specific examples of the aromatic monoalcohol (B) include alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tertiary butylphenol; o-phenyl Aralkylphenols such as phenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol and 4-(α-cumyl)phenol; and naphthol compounds such as 1-naphthol and 2-naphthol. Among these, o-cresol and naphthol are preferable as the aromatic monoalcohol (B) from the viewpoint of better dielectric properties.
The aromatic monoalcohol (B) may be used alone or in combination of two or more.

-Phosphorus-containing polyhydric alcohol compound (C)-
In the present embodiment, the phosphorus-containing polyhydric alcohol compound (C) is preferably a compound containing a phosphorus atom and having at least two hydroxyl groups. Phosphorus-containing polyhydric alcohol compounds (C) therefore also include phosphoric acid, phosphorous and phosphoric acid esters. In addition, phosphorus in the phosphorus-containing polyhydric alcohol compound (C) is particularly limited, such as the valence of phosphorus (-3, -1, +1, +3, +5) and the bonding form of phosphorus, as long as it is in a form that exhibits flame retardancy. However, for example, it preferably exists in the form of pentavalent phosphorus in which an oxo group (=O) is directly bonded to a phosphorus atom, that is, as an oxoline (V) group (≡P(=O).
Moreover, the hydroxyl equivalent of the phosphorus-containing polyhydric alcohol compound (C) in the present embodiment is required to be less than 1000 g/eq. The hydroxyl equivalent is preferably 50 g/eq or more and less than 800 g/eq, more preferably 100 g/eq or more and less than 500 g/eq. When the hydroxyl equivalent is less than 500 g/eq, the cured product is excellent from the viewpoint of heat resistance. In addition, the said hydroxyl-group equivalent is a value measured based on JISK0070.
The valence (number) of hydroxyl groups in the phosphorus-containing polyhydric alcohol compound (C) is preferably divalent to hexavalent, more preferably divalent.

［上記一般式（ＩＩ）中、Ｍ^１ＩＩは一価～六価の炭化水素基を表し、Ｒ^３ＩＩ及びＲ^４ＩＩはそれぞれ独立して、一価～二価の炭化水素基を表し、Ｒ^３ＩＩ又はＲ^４ＩＩが互いに結合した環状構造を形成してもよく、ｎｃ１は２～５の整数を表す。］を表すことが好ましい。なお、上記一般式（ＩＩ）は、上記一般式（ｃ１）に対応する。そのため、上記一般式（ＩＩ）中のＲ^３ＩＩ－（Ｒ^４ＩＩ）Ｐ（＝Ｏ）－Ｍ^１ＩＩ－の部分構造が、Ａ^ｃ１でありうる。
リン含有多価アルコール化合物（Ｃ）は、市販されているものを用いてもよい。市販品は、例えば、三光株式会社製のＨＣＡ－ＨＱ（１０－(２，５－ジヒドロキシフェニル)－９，１０-ジヒドロ９－オキサ－１０－フォスファフェナントレン－１０－オキサイド）や、ＨＣＡ＝ＮＱ（１０－[２－(ジヒドロキシナフチル)]－９,１０－ジヒドロ－９－オキサ－１０－フォスファフェナントレン－１０－オキサイド）、日本化学工業株式会社製ＣＰＨＯ－ＨＱ（１，４－シクロオクチレンホスホニル－１，４－ハイドロキノン及び１，５－シクロオクチレンホスホニル－１，４－ハイドロキノンの混合物）、ＨＣＡ－マレイン酸付加物・ＨＣＡ－シトラコン酸付加物・ＨＣＡ－イタコン酸付加物（商品名Ｍ－ＡＣＩＤ、三光（株）製）などのリン含有ジカルボン酸モノマー等が挙げられる。
また、リン含有多価アルコール化合物（Ｃ）におけるリン含有量は、３質量％以上であることが好ましく、４～２５質量％の範囲であることがより好ましい。
リン含有量が上記範囲であると、生成物であるリン含有活性エステルの難燃性効果を期待することができる。また、リン含有量の測定方法は、実施例の欄に記載の方法を用いて算出している。 The phosphorus-containing polyhydric alcohol compound (C) may or may not contain an aromatic ring, and preferably contains an aromatic ring. In addition, the phosphorus-containing polyhydric alcohol compound (C) has a phosphorus atom and two or more hydroxyl groups, and has a linear or branched alkylene chain (divalent aliphatic hydrocarbon group), a linear or A compound having a branched alkylene ether chain (alkyleneoxy group) or a hydrocarbon group having an aromatic ring is preferred.
Specifically, the phosphorus-containing polyhydric alcohol compound (C) has the following general formula (II):

[In the above general formula (II), M ^1II represents a monovalent to hexavalent hydrocarbon group, R ^3II and R ^4II each independently represent a monovalent to divalent hydrocarbon group, and R ^3II or R ^4II may be bonded together to form a cyclic structure, and nc1 represents an integer of 2-5. ] is preferably represented. The general formula (II) above corresponds to the general formula (c1) above. Therefore, the partial structure of R ^3II -(R ^4II )P(=O)-M ^1II - in the general formula (II) can be A ^c1 .
A commercially available product may be used as the phosphorus-containing polyhydric alcohol compound (C). Commercially available products include, for example, HCA-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) manufactured by Sanko Co., Ltd. and HCA=NQ (10-[2-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), Nippon Chemical Industry Co., Ltd. CPHO-HQ (1,4-cyclooctylene mixture of phosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone), HCA-maleic acid adduct, HCA-citraconic acid adduct, HCA-itaconic acid adduct (product Phosphorus-containing dicarboxylic acid monomers such as M-ACID (manufactured by Sanko Co., Ltd.) and the like can be mentioned.
The phosphorus content in the phosphorus-containing polyhydric alcohol compound (C) is preferably 3% by mass or more, more preferably in the range of 4 to 25% by mass.
When the phosphorus content is within the above range, the resulting phosphorus-containing active ester can be expected to have a flame retardant effect. Moreover, the method for measuring the phosphorus content is calculated using the method described in the Examples section.

-Ether bond-containing aliphatic compound (D)-
In the present embodiment, the ether bond-containing aliphatic compound (D) (compound having a partial structure represented by R ¹ and / or R ² in the general formula (1)) is an aliphatic compound having one or more ether bonds cyclic ethers (alkylene oxides), carbonate compounds, or alkylene polyols, with cyclic ethers (alkylene oxides), carbonate compounds, or alkylene polyols being preferred.
Cyclic ethers (alkylene oxides) include compounds having an epoxy group such as ethylene oxide, propylene oxide and butylene oxide.
Carbonate compounds include ethylene carbonate, propylene carbonate, butylene carbonate, and the like.
Preferred alkylene polyols are aliphatic polyols such as ethylene glycol (number average molecular weight: 62), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. , 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, linear aliphatic diol compounds such as 1,12-dodecanediol; propylene glycol, 2- methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-14-butanediol, 2,3-dimethyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3,3- Dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol, 2,4- Diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,5-diethyl-1,6-hexanediol, etc. trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, and other trifunctional or higher aliphatic polyol compounds. These aliphatic polyol compounds may be used alone or in combination of two or more.

In the present embodiment, as reaction raw materials, aromatic polycarboxylic acids, acid halides and/or esters thereof (A), aromatic monoalcohols (B), phosphorus-containing polyhydric alcohol aromatic compounds (C) or If necessary, it may further contain a compound (F) that exhibits reactivity with the ether bond-containing aliphatic compound (D).
Examples of the compound (F) include m-dihydroxybenzene, 2,4-toluenediol, 3,5-toluenediol, p-xylene-2,6-diol, m-xylene-4,6-diol, p-dihydroxy Benzene, 2,5-toluenediol, p-xylene-2,5-diol, dihydroxynaphthalene, dihydroxyanthracene and other polyaromatics.
The content of the compound (F) or the group derived from the compound (F) is, for example, preferably 30% by mass or less with respect to the total amount (100% by mass) of the phosphorus-containing active ester, and 20% by mass. % or less, more preferably 10 mass % or less.

［上記一般式（１’）中、Ａはそれぞれ独立して、二価の炭化水素基を表し、Ｒ^１１及びＲ^１２はそれぞれ独立して、直鎖状又は分岐状のアルキレン基を表し、
Ｑ^１１及びＱ^１２はそれぞれ独立して、二価の芳香族基を表し、
Ａｒ^１１及びＡｒ^１２はそれぞれ独立して、下記一般式（２）又は（３）：

［上記一般式（２）及び一般式（３）中の＊は、上記一般式（１）中のＡｒ^１１又はＡｒ^１２と結合する酸素原子との結合手を表し、
Ｒ^２１及びＲ^３１はそれぞれ独立して、ハロゲン原子、アルキル基、アルケニル基（アリル基等）、アルコキシ基、アリール基又はアラルキル基を表し、ｋ^２１は、０～７の整数を表し、ｋ^３１は、０～５の整数を表す。］で示される構造を表し、
ｘ^１は、０．１以上の平均繰り返し数であり、ｙ^１は、１以上の平均繰り返し数であり、ｚ^１は、１以上の平均繰り返し数である。］で表される化合物である。
上記一般式（１’）で表されるリン含有活性エステルは、複数のエステル結合を有し、かつ極性が比較的に低い、鎖状のアルキレン基又はアルキレンエーテル基を含むため、柔軟セグメントとして機能しやすくなり、密着性又は低誘電特性に優れた硬化物を得ることができ、有用である。
本実施形態のリン含有活性エステルのより好ましい形態の一例は、上記一般式（１’）で表され、上記一般式（１’）中、Ａはそれぞれ独立して、芳香族基を表し、Ｒ^１１及びＲ^１２はそれぞれ独立して、直鎖状又は分岐状のアルキレン基を表し、Ｑ^１１及びＱ^１２はそれぞれ独立して、１，３－フェニレン基、１，４－フェニレン基を表し、ｘ^１は０．０１以上１０以下の平均繰り返し数を表し、ｙ^１は、１以上の平均繰り返し数であり、ｚ^１は、１以上の平均繰り返し数であり、
Ａｒ^１１及びＡｒ^１２はそれぞれ独立して、上記一般式（２）又は（３）で示される構造を表し、上記一般式（２）及び一般式（３）中の＊は、上記一般式（１）中のＡｒ^１１又はＡｒ^１２と結合する酸素原子との結合手を表し、
Ｒ^２１及びＲ^３１はそれぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリール基又はアラルキル基のいずれかを表し、ｋ^２１は、０～７の整数を表し、ｋ^３１は、０～５の整数を表す。］で表されることが好ましい。 As described above, the phosphorus-containing active ester in the present disclosure includes an aromatic compound (A) having a carboxylic acid halogen group, an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol aromatic compound (C), and an ether bond. It is a compound that uses the contained aliphatic compound (D) as a reaction raw material. On the other hand, when the phosphorus-containing active ester in the present disclosure is specified by another expression independent of the reaction raw material, the phosphorus-containing active ester of the present embodiment has the following general formula (1′):

[In the above general formula (1′), A each independently represents a divalent hydrocarbon group, R ¹¹ and R ¹² each independently represent a linear or branched alkylene group,
Q ¹¹ and Q ¹² each independently represent a divalent aromatic group,
Ar ¹¹ and Ar ¹² are each independently represented by the following general formula (2) or (3):

[* in the above general formulas (2) and (3) represents a bond with the oxygen atom that binds to Ar ¹¹ or Ar ¹² in the above general formula (1),
R ²¹ and R ³¹ each independently represent a halogen atom, an alkyl group, an alkenyl group (such as an allyl group), an alkoxy group, an aryl group or an aralkyl group; k ²¹ represents an integer of 0 ^to 7; represents an integer from 0 to 5. ] Represents a structure represented by
^x1 is an average repetition number of 0.1 or more, ^y1 is an average repetition number of 1 or more, and ^z1 is an average repetition number of 1 or more. ] It is a compound represented by.
The phosphorus-containing active ester represented by the general formula (1′) contains a chain alkylene group or alkylene ether group having a plurality of ester bonds and relatively low polarity, so it functions as a flexible segment. It is useful because it becomes easier to cure and a cured product having excellent adhesion or low dielectric properties can be obtained.
An example of a more preferable form of the phosphorus-containing active ester of the present embodiment is represented by the general formula (1 '), in which each A independently represents an aromatic group, and R ¹¹ and R ¹² each independently represent a linear or branched alkylene group, Q ¹¹ and Q ¹² each independently represent a 1,3-phenylene group or a 1,4-phenylene group, x ¹ represents an average repetition number of 0.01 or more and 10 or less, y ¹ is an average repetition number of 1 or more, z ¹ is an average repetition number of 1 or more,
Ar ¹¹ and Ar ¹² each independently represent a structure represented by the general formula (2) or (3), and * in the general formulas (2) and (3) represents the general formula (1 ) represents a bond with the oxygen atom that binds to Ar ¹¹ or Ar ¹² in
R ²¹ and R ³¹ each independently represent a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl ^group or an aralkyl group; k ²¹ represents an integer of 0 to 7; Represents an integer from 0 to 5. ] is preferably represented.

<Another Preferred Form of Phosphorus-Containing Active Ester>
Another preferable form of the phosphorus-containing active ester of the present embodiment is an ester compound (a') (also referred to as an intermediate product (a')), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing compound and an intermediate product (b') which is a reaction product of and a reaction product of the reaction raw material (I). The intermediate product (a') is an aromatic polycarboxylic acid, an acid halide thereof and/or an esterified product thereof (A), an aromatic monoalcohol (B), and a reaction raw material (II). It can also be a reaction product that Furthermore, the intermediate product (b') can also be a reaction product of the phosphorus-containing polyhydric alcohol compound (C) and the ether bond-containing compound (D) as reaction raw materials (III).
An ester compound (a') in which an ester bond is formed is obtained by reacting the aromatic polycarboxylic acid (A) and the aromatic monoalcohol (B). Then, by reacting the phosphorus-containing polyhydric alcohol compound (C) with the ether bond-containing compound, an intermediate product (b') having two or more ether bond-forming hydroxyl groups is obtained.
On the other hand, by reacting the ester compound (a') with the intermediate product (b'), a transesterification reaction occurs, and a group containing an aromatic ring at the end (e.g., an aryloxycarbonyl group) containing a phosphorus Contained active esters can be obtained.

In the present embodiment, the use of the phosphorus-containing active ester is a preferable mode because a cured product having a low dielectric loss tangent and excellent flame retardancy, heat resistance, moist heat resistance, and adhesion can be obtained. The reason for this is not necessarily clear, but since the obtained phosphorus-containing active ester contains an aryloxycarbonyl group (active ester group) at its terminal, it exhibits high reactivity with the epoxy group possessed by the epoxy resin described later. Due to the high reactivity, it is possible to prevent or suppress the generation of hydroxyl groups caused by ring-opening of epoxy groups, which is a preferred embodiment. In addition, since the phosphorus-containing active ester has no or almost no hydroxyl groups in the molecule, even in the cured product obtained by the reaction of the phosphorus-containing active ester, hydroxyl groups derived from the phosphorus-containing active ester have no or little Such an active ester can prevent or suppress the generation of hydroxyl groups during curing. In general, hydroxyl groups with high polarity are known to increase the dielectric loss tangent, but by using the phosphorus-containing active ester, it is possible to achieve a low dielectric loss tangent in the cured product, which is particularly useful.

In addition, since the phosphorus-containing active ester has two or more ester bonds reactive with the epoxy group of the epoxy resin to be described later, the crosslink density of the cured product can be increased and the heat resistance can be improved.

The phosphorus-containing active ester of the present embodiment has a flexible segment such as an alkylene group or an alkyleneoxy group (alkylene ether chain) and has no or almost no hydroxyl group, so it has a low polarity structure. A curable composition ( For example, an epoxy resin composition containing an epoxy resin), and furthermore, a cured product, an insulating material, a resist material, and the like obtained by using the curable composition can be provided, which is a preferred embodiment.

<Characteristics of phosphorus-containing active ester>
The functional group equivalent of the phosphorus-containing active ester of the present embodiment is excellent in curability, low dielectric constant and dielectric It is preferably in the range of 160 to 1500 g/eq, more preferably in the range of 180 to 1200 g/eq, and more preferably in the range of 200 to 1000 g/eq, because a cured product with tangent (low dielectric properties) can be obtained. It is even more preferred to have
The phosphorus content in the phosphorus-containing active ester of the present embodiment is preferably 1.8% by mass or more from the viewpoint of flame retardancy and low dielectric loss tangent of the resulting cured product, and 1.8 to 25% by mass. more preferably 1.9 to 24% by mass.
The number average molecular weight (Mn) of the phosphorus-containing active ester of the present disclosure is preferably 320-3000, more preferably 360-2400. A number average molecular weight (Mn) of 320 or more is preferable because the dielectric loss tangent is excellent. On the other hand, when the number average molecular weight (Mn) is 3000 or less, it is preferable because moldability is excellent.
The method for measuring the functional group equivalent weight, phosphorus content and number average molecular weight (Mn) of the phosphorus-containing active ester is calculated using the methods described in Examples.
As the phosphorus-containing active ester of the present embodiment, the phosphorus-containing active ester is used from the viewpoint of better balance between handling properties when preparing a curable composition described later, excellent elongation of the cured product, and dielectric properties. The softening point of the ester is preferably 200°C or lower, more preferably 180°C or lower. Also, the softening point of the phosphorus-containing active ester of the present embodiment is measured according to JIS K7234.

The phosphorus-containing active ester of this embodiment includes a rigid mesogen having an aromatic ring linked by an ester bond, a flexible segment such as an alkylene chain or an alkylene ether chain,
A phosphorus-containing group exhibiting flame retardancy (preferably a mesogen having an oxoline (V) group (≡P(=O))), and does not have or substantially does not have a hydroxyl group , a curable composition that has a low polarity structure and can exhibit excellent elongation, adhesion to copper foil due to flexibility, and low dielectric properties in the resulting cured product ( For example, an epoxy resin composition containing an epoxy resin), and further, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a build-up film, etc. using the curable composition can be provided.

<Method for Synthesizing Phosphorus-Containing Active Ester>
As a method for synthesizing the phosphorus-containing active ester described above, the above-described aromatic polycarboxylic acids (A), aromatic monoalcohols (B), phosphorus-containing polyhydric alcohol compounds (C) and ether bond-containing aliphatic compounds (D ) as a starting material for the reaction. However, in the synthesis of the phosphorus-containing active ester described above,
(1) A first reaction step of reacting an aromatic polycarboxylic acid (A) and an aromatic monoalcohol (B) to obtain an intermediate product (a'), and
(2) a second reaction step of reacting a phosphorus-containing polyhydric alcohol compound (C) with an ether bond-containing aliphatic compound (D) to obtain an intermediate product (b');
(3) a third reaction step of reacting the intermediate product (a') with the intermediate product (b') to obtain a phosphorus-containing active ester as a reaction product;
It is preferred to use a method comprising This is because the phosphorus-containing active ester can be obtained relatively easily.
In this case, in the first reaction step, an ester compound in which an ester bond is formed is obtained as an intermediate product (a′), and in the second reaction step, the hydroxyl group of the phosphorus-containing polyhydric alcohol compound (C) contains an ether bond. An ether compound having a terminal hydroxyl group to which -O-hydrocarbon group- (eg, oxy-alkylene) of the aliphatic compound (D) is added/condensed is obtained as an intermediate product (b'), followed by a third reaction In the process, a transesterification reaction can occur to obtain a phosphorus-containing active ester containing an aryloxycarbonyl group structure at the terminal.

The conditions for the first reaction step are not particularly limited, but for example, the reaction can be carried out in the presence of an alkali catalyst at a temperature of 60° C. or less for a reaction time of 1 to 24 hours. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These alkali catalysts may be used singly or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferable as the alkali catalyst because of its high reaction efficiency. The alkali catalyst may be used as a 3-30% aqueous solution. Moreover, in this case, an interlayer transfer catalyst may be used in order to increase the reaction efficiency. Examples of interlayer transfer catalysts include alkylammonium salts and crown ethers. These interlayer transfer catalysts may be used singly or in combination of two or more.

The first reaction step is preferably carried out in an organic solvent because it facilitates reaction control. Examples of the organic solvent include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, butyl acetate and cellosolve acetate. , propylene glycol monomethyl ether acetate, carbitol acetate and other acetate solvents, cellosolve, butyl carbitol and other carbitol solvents, toluene, xylene and other aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other amide-based solvents. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

The reaction ratio of the aromatic polycarboxylic acids (A) and the aromatic monoalcohol (B) can be appropriately changed according to the desired molecular design. However, from the viewpoint of reducing excess reaction raw materials while reducing unreacted terminals, the aromatic monoalcohol (B) is 1.1 to 5 per 1 mol of the aromatic polycarboxylic acids (A). 0 mol, more preferably 1.5 to 4.0 mol, even more preferably 2.0 to 3.0 mol.

After completion of the first reaction step, when an aqueous solution is used in the presence of an alkali catalyst, the reaction solution is allowed to stand still for liquid separation to remove the aqueous layer, the remaining organic layer is washed with water, and the aqueous layer is almost in the middle. The aromatic polyvalent carboxylic acid (A) and the aromatic monoalcohol (B) in which the content of inorganic salts that have an adverse effect on insulation is reduced by repeating water washing until the pH reaches about 7, and the aromatic monoalcohol (B) Intermediate product (a') which is a reaction product of can be obtained. This makes it possible to reduce the inorganic salt content that adversely affects the insulating properties in the obtained intermediate product (a').

Next, in the second reaction step, the phosphorus-containing polyhydric alcohol compound (C) and the ether bond-containing aliphatic compound (D) are heated and stirred under a base catalyst to obtain an intermediate product (b'). For example, the condensation reaction between the phosphorus-containing polyhydric alcohol compound (C) represented by the general formula (II) and a cyclic ether or carbonate compound, phosphoric acid, phosphonic acid, phosphinic acid, phosphane oxide, phosphorous acid, Condensation reaction of at least one phosphoric acid selected from the group consisting of phosphonic acid and phosphinic acid and alkylene polyol, or HCA-maleic acid adduct, HCA-citraconic acid adduct, HCA-itaconic acid adduct (product An intermediate product (b') can be obtained by condensation reaction of a phosphorus-containing polyhydric alcohol compound (C) such as M-ACID (manufactured by Sanko Co., Ltd.) and an alkylene polyol. As the intermediate product (b'), a commercially available product (hydroxyl-terminated phosphorus-containing polyester polyol condensate (trade name: M-ESTER, ME-P8 manufactured by Sanko Co., Ltd.)) may be used.
Examples of basic catalysts used in the second reaction step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine, pyridine, diazabicycloundecene, diazabicycloundecene, Zabicyclononene, triphenylphosphine and the like can be mentioned. These base catalysts may be used alone or in combination of two or more types, and diazabicycloundecene, diazabicyclononene, and triphenylphosphine are preferred because of their high reaction efficiency.
The second reaction step is not particularly limited, but may be carried out without a solvent (no organic solvent is used) or in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. Acetate solvents such as ether acetate and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Solvents can be mentioned. Each of these organic solvents may be used alone, or two or more of them may be used as a mixed solvent.
The conditions for the second reaction step are not particularly limited, but for example, the intermediate product (b') can be obtained by stirring and reacting for 1 to 24 hours under temperature conditions of 50 to 250°C. can be done.
The intermediate product (b') may have a structure in which the hydrogen atoms of the hydroxyl groups of the phosphorus-containing polyhydric alcohol compound (C) are substituted with alkylene oxides such as alkylene polyols.

In the third reaction step, the intermediate product (a') obtained in the first reaction step and the intermediate product (b') obtained in the second reaction step are reacted. This causes a transesterification reaction to obtain the phosphorus-containing active ester of the present disclosure. The conditions for the third reaction step are not particularly limited, but for example, stirring and reaction can be carried out at a temperature of 50 to 250° C. for 1 to 24 hours. In the second reaction step, alkali catalysts, especially amine catalysts (alkylamines such as triethylamine, triphenylamine, etc. and arylamines, condensed ring amines such as DBU and DBN, heterocyclic amines such as imidazole and pyridine) are used. The addition can promote the reaction.

During the reaction in the third reaction step, an antioxidant may be used in order to prevent deterioration due to inclusion of a trace amount of oxygen. Specific examples of antioxidants include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4′-dialkoxy-2,2′-bi-1-naphthol, 3-(N -salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine , 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, “4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-1 ,6-di-tert-butylphenol and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like. quinone compounds, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.N''-diphenyl-p-phenylenediamine, Ni-propyl-N''-phenyl-p-phenylenediamine, N-(1. 3-dimethylbutyl)-N''-phenyl-p-phenylenediamine, diphenylamine, 4,4''-dicumyl-diphenylamine, 4,4''-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1 ,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, amine compounds, phenothiazine, di Stearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecan-1-yl=3 , thioether compounds such as 3′-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N, N-Dimethyl p-Nitrosoaniline, p-Nitrosodiphenylamine, p-Nitrondimethylamine, p-Nitron-N, N-diethylamine, N-Nitrosoethanolamine, N-Nitrosodi-n-butylamine, N-Nitroso-Nn -butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso N-phenyl hydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn-propylurethane, 1-nitroso-2-naphthol , 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride , nitroso compounds such as 2-nitroso-5-methylaminophenol hydrochloride, esters of phosphoric acid and octadecan-1-ol, triphenylphosphite, 3,9-diotadecan-1-yl-2,4,8, 10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, trisnonylphenylphosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2 - Phosphite compounds such as ethylhexyl diphenyl phosphite, diphenylisodecylphosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(dimethyldithiocarbamate-κ(2 ) S, S′) zinc, zinc compounds such as zinc diethyldithiocarbamate, zinc dibutyl-dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S′) nickel, 1,3- Dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octane-1-ylsulfanyl)methyl]phenol, dilauryl Examples thereof include sulfur compounds such as thiodipropionate and distearyl 3,3'-thiodipropionate. These antioxidants can be used alone or in combination of two or more.
Commercially available products of the antioxidant include, for example, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd. is mentioned.
In the third reaction step, the same solvent as used in the first reaction step can be used.

The reaction ratio of the intermediate product (a') and the intermediate product (b') can be appropriately changed according to the desired molecular design. However, from the viewpoint of improving excellent adhesion, excellent elongation and low dielectric properties in a well-balanced manner, the hydroxyl group equivalent of the intermediate product (b') with respect to 1 equivalent of the active ester group of the intermediate product (a') is , preferably in the range of 0.1 to 0.9 mol, more preferably in the range of 0.2 to 0.8 mol, even more preferably in the range of 0.3 to 0.8 mol .

After completion of the reaction in the second reaction step, atmospheric distillation or vacuum distillation (for example, 0.9 to 0.01 atm) is preferably carried out in order to remove excess aromatic monoalcohol (B). Thereby, the purity of the obtained phosphorus-containing active ester can be increased.

(Resin having an acid group and a polymerizable unsaturated group)
The resin composition of this embodiment contains a resin having an acid group and a polymerizable unsaturated group as an essential component. Examples of the resin having an acid group and a polymerizable unsaturated group of the present embodiment include the following [1] to [6]:
[1] an epoxy resin (B1) having an acid group and a polymerizable unsaturated group,
[2] Urethane resin (B2) having an acid group and a polymerizable unsaturated group
[3] a (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group,
[4] an amideimide resin (B4) having an acid group and a polymerizable unsaturated group,
[5] an acrylamide resin (B5) having an acid group and a polymerizable unsaturated group,
[6] an ester resin (B6) having an acid group and a polymerizable unsaturated group,
and the like. The epoxy resin (B1) to the urethane resin (B6) will be described in order below.

<Epoxy Resin (B1) Having Acid Group and Polymerizable Unsaturated Group>
Examples of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment include epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride ( Epoxy (meth)acrylate resins having an acid group with b1-3) as essential reaction raw materials, epoxy resins (b1-1), unsaturated monobasic acids (b1-2), polybasic acid anhydrides (b1- 3), a polyisocyanate compound (b1-4), and an epoxy (meth)acrylate resin having an acid group and a urethane bond using a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials.

The specific structure of the epoxy resin (b1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, Biphenyl-type epoxy resin, triphenylmethane-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol novolac-type epoxy resin, naphthol novolac-type epoxy resin, naphthol-phenol co-condensation novolak-type epoxy resin, naphthol-cresol co- Condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin , trihydroxybenzene-type epoxy resins, oxazolidone-type epoxy resins, and the like. These epoxy resins can be used alone or in combination of two or more.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin. Resin etc. are mentioned.
Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Resin etc. are mentioned.
Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, tetramethyl-2,2' - Biphenol-type epoxy resin and the like.
Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4′-biphenol type epoxy resin, hydrogenated 2,2′-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4′-biphenol type epoxy resin. , hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.
The epoxy resin (b1-1) can be used alone or in combination of two or more.

［上記一般式（４）中、Ｘ^４１は、炭素数１～１０のアルキレン鎖、ポリオキシアルキレン鎖、（ポリ）エステル鎖、芳香族炭化水素鎖、又は（ポリ）カーボネート鎖を表し、Ｘ^４１の構造中の水素原子がハロゲン原子又はアルコキシ基に置換されてもよく、Ｙ^４１は、水素原子又はメチル基である。］ The unsaturated monobasic acid (b1-2) includes, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Acid halides and esters of the above unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (4) can also be used.

[In the above general formula (4), X ⁴¹ represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain, and X ⁴¹ A hydrogen atom in the structure of may be substituted with a halogen atom or an alkoxy group, and Y ⁴¹ is a hydrogen atom or a methyl group. ]

［上記一般式（５）中、Ｒ^５１及びＲ^５２は、炭素原子数１～１０のアルキレン基を表し、ｎは１～５の整数を表す。］ Examples of the polyoxyalkylene chain include polyoxyethylene chain and polyoxypropylene chain.
Examples of the (poly)ester chain include a (poly)ester chain represented by the following general formula (5).

[In general formula (5) above, R ⁵¹ and R ⁵² represent an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5. ]

［上記一般式（６）中、Ｒ^６１は、炭素原子数１～１０のアルキレン基を表し、ｎ^６１は１～５の整数を表す。］
一般式（４）で表される化合物の分子量は、１００～５００の範囲が好ましく、１５０～４００の範囲がより好ましい。
不飽和一塩基酸（ｂ１－２）は、単独で用いることも２種以上を併用することもできる。 Examples of the aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, binaphthylene chains, and the like. A hydrocarbon chain having an aromatic ring such as a benzene ring, naphthalene ring, anthracene ring, or phenanthrene ring can also be used as a partial structure.
Examples of the (poly)carbonate chain include a (poly)carbonate chain represented by the following general formula (6).

[In the general formula (6), R ⁶¹ represents an alkylene group having 1 to 10 carbon atoms, and n ⁶¹ represents an integer of 1 to 5. ]
The molecular weight of the compound represented by formula (4) is preferably in the range of 100-500, more preferably in the range of 150-400.
The unsaturated monobasic acid (b1-2) can be used alone or in combination of two or more.

Examples of polybasic acid anhydrides (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, and acid halogens of aliphatic polybasic acid anhydrides. acid halides, alicyclic polybasic acid anhydride acid halides, aromatic polybasic acid anhydride acid halides, and the like.

Examples of the aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, and itaconic acid. acids, glutaconic acid, acid anhydrides of 1,2,3,4-butanetetracarboxylic acid, and the like. In addition, the aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight chain type or a branched type, and may have an unsaturated bond in its structure.
As the above-mentioned alicyclic polybasic acid anhydride, in the present disclosure, an alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and an aromatic ring at a structural site other than that is It does not matter whether or not Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2, 3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene- Examples include acid anhydrides of 1,2-dicarboxylic acids.
Examples of the aromatic polybasic acid anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, An acid anhydride of benzophenonetetracarboxylic acid and the like can be mentioned.
Polybasic acid anhydrides (b1-3) can be used alone or in combination of two or more. In addition, among these, tetrahydrophthalic anhydride, succinic anhydride, cyclohexanedicarboxylic acid can be obtained, since a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner can be obtained. Acid anhydrides are preferred.

［上記一般式（７）中、Ｒ^１３及びＲ^１５はそれぞれ独立して、水素原子又は炭素原子数１～６の一価の炭化水素基のいずれかを表し、Ｒ^１５はそれぞれ独立して、炭素原子数１～４のアルキル基を表し、ｉ７は０又は１～３の整数であり、ｍは１以上の整数である。］ Examples of the polyisocyanate compound (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate , isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other alicyclic diisocyanate compounds; - Aromatic diisocyanate compounds such as diisocyanato-3,3'-dimethylbiphenyl and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (7); Examples include biuret-modified products and allophanate-modified products.
The polyisocyanate compound (b1-4) can be used alone or in combination of two or more.

[In the above general formula (7), R ¹³ and R ¹⁵ each independently represent either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ¹⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, i7 is 0 or an integer of 1 to 3, and m is an integer of 1 or more. ]

The (meth)acrylate compound (b1-5) having a hydroxyl group includes, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, penta Erythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipenta Erythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and the like. In addition, (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structures of the (meth)acrylate compounds having various hydroxyl groups. (Poly)oxyalkylene modified products, lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various hydroxyl group-containing (meth)acrylate compounds, and the like can also be used.
Among these, those having a molecular weight of 1,000 or less are preferable because a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner can be obtained. Further, when the hydroxyl group-containing (meth)acrylate compound (b1-4) is an oxyalkylene modified product or a lactone modified product, the weight average molecular weight (Mw) is preferably 1,000 or less.
The (meth)acrylate compound (b1-4) having a hydroxyl group can be used alone or in combination of two or more.

The method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment is not particularly limited, and any method may be used. The production of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
In the present embodiment, the method for producing an epoxy resin (B1) having an acid group and a polymerizable unsaturated group includes epoxy resin (b1-1), unsaturated monobasic acid (b1-2), and polybasic acid anhydride. (b1-3) as an essential reaction raw material, or epoxy resin (b1-1), unsaturated monobasic acid (b1-2), polybasic acid anhydride (b1-3), polyisocyanate compound ( b1-4) and a (meth)acrylate compound (b1-5) having a hydroxyl group are not particularly limited as long as they are reaction raw materials. For example, the epoxy resin (B1) may be produced by a method of reacting all of the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the epoxy resin (b1-1) is first reacted with the unsaturated monobasic acid (b1-2), and then the polybasic acid anhydride (b1-3). is preferably reacted. The reaction is performed, for example, by reacting an epoxy resin (b1-1) and an unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature range of 100 to 150° C., and then entering the reaction system. It can be carried out by a method of adding polybasic acid anhydride (b1-3) and reacting at a temperature range of 80 to 120°C.
In the present embodiment, the reaction ratio between the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) is the unsaturated monobasic acid per mole of epoxy groups in the epoxy resin (b1-1). (b1-2) is preferably used in the range of 0.9 to 1.1 mol. Further, the reaction ratio of the polybasic acid anhydride (b1-3) is preferably in the range of 0.2 to 1.0 mol per 1 mol of epoxy groups in the epoxy resin (b1-1).

Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; Cyclic ether solvents; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatic solvents such as toluene, xylene and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol and propanol , isopropanol, butanol, cyclohexanol, propylene glycol monomethyl ether and other alcohol solvents; propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol and other ether solvents; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, di Glycol ether solvents such as alkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; be done. These organic solvents can be used alone or in combination of two or more.

In addition, as the organic solvent, a commercial product can also be used, and examples of the commercial product include "No. 1 spindle oil", "No. 3 solvent", "No. 4 solvent" and "No. 5 Solvent", "Solvent No. 6", "Naphthesol H", "Alkene 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7", manufactured by Mitsubishi Chemical Corporation "Diadol 13", "Dialen 168"; Nissan Chemical Co., Ltd. "F Oxocol", "F Oxocol 180"; Idemitsu Kosan Co., Ltd. "Supersol LA35", "Supersol LA38"; ExxonMobil Chemical Co., Ltd. "Exsol D80" ”, “Exsol D110”, “Exsol D120”, “Exsol D130”, “Exsol D160”, “Exsol D100K”, “Exsol D120K”, “Exsol D130K”, “Exsol D280”, “Exsol D300”, “Exsol D320 "; and the like.
The above organic solvents can be used alone or in combination of two or more. Further, in the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since the reaction efficiency is improved.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene- 5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-( 2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium acetate, etc. ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; Phosphonium salts such as chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; Organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; Organometallic compounds such as zinc octylate and bismuth octylate; Inorganic tin compounds such as tin octoate; etc. Alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides and the like can also be used.
The above basic catalysts may be used alone or in combination of two or more. Moreover, the amount of the basic catalyst to be added is preferably in the range of 0.001 to 5 parts by mass with respect to the total of 100 parts by mass of the reaction raw materials.

In the present embodiment, the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is a curing capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner. A range of 30 to 150 mgKOH/g is preferable, and a range of 40 to 120 mgKOH/g is more preferable, since a stable composition can be obtained. In addition, in the present disclosure, the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is a value measured by the neutralization titration method of JIS 0070 (1992).

<Urethane Resin (B2) Having Acid Group and Polymerizable Unsaturated Group>
Examples of the urethane resin (B2) having an acid group and a polymerizable unsaturated group of the present embodiment include a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), and a carboxyl group-containing polyol. obtained by reacting the compound (b2-1), and optionally the polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1) Resin; other than polyisocyanate compound (b1-4), hydroxyl group-containing (meth)acrylate compound (b1-5), polybasic acid anhydride (b1-3), and carboxyl group-containing polyol compound (b2-1) and a resin obtained by reacting a polyol compound (b2-2); or an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3 ), a polyisocyanate compound (b1-4), and a hydroxyl group-containing (meth)acrylate compound (b1-5).

Examples of the carboxyl group-containing polyol compound (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more.
Examples of the polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1) include ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, di Aliphatic polyol compounds such as pentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structures of the various polyol compounds (poly)oxyalkylene modified products into which a (poly)oxyalkylene chain is introduced such as; and lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds described above. Polyol compounds other than the carboxyl group-containing polyol compound can be used alone or in combination of two or more.

The method for producing the urethane resin (B2) having an acid group and a polymerizable unsaturated group in the present embodiment is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary.
As the organic solvent, the same organic solvent as described in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used. It is also possible to use two or more kinds in combination. As the basic catalyst, the same basic catalyst as described in the section <Epoxy resin having an acid group and a polymerizable unsaturated group (B1)> can be used. can be used alone or in combination of two or more.

<(Meth)acrylate Resin (B3) Having Acid Group and Polymerizable Unsaturated Group>
The (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in the present embodiment may have an acid group and a (meth)acrylate group, and the hydrogen atom of the carboxylic acid is an alkyl group. Obtained by polymerizing a (meth)acrylate compound (α) containing a substituted (meth)acrylate ester and having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group (α) as an essential component ( A reaction product obtained by introducing a (meth)acryloyl group by further reacting a (meth)acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group capable of reacting with these functional groups. or a resin obtained by reacting a hydroxyl group in the reaction product with a polybasic acid anhydride (b1-3).

In the present embodiment, the (meth)acrylic resin intermediate may be obtained by copolymerizing other polymerizable unsaturated group-containing compounds in addition to the (meth)acrylate compound (α) as necessary. . The other polymerizable unsaturated group-containing compounds are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (meth) Alkyl acrylic esters; Alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Aromatic ring-containing (meth)acrylates such as ethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene.
Other polymerizable unsaturated group-containing compounds can be used alone or in combination of two or more.

The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α). is preferred. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β).
The (meth)acrylate compound (β) can be used alone or in combination of two or more.

The method for producing the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in the present embodiment is not particularly limited, and any method may be used. In the production of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group, it may be carried out in an organic solvent if necessary, or if necessary using a basic catalyst. good.
As the organic solvent, the same organic solvent as described in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the organic solvent is used alone. It is also possible to use two or more kinds in combination.
As the basic catalyst, the same basic catalyst as described in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the basic catalyst is Using independently can also use 2 or more types together.

The acid value of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in the present embodiment is capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner. A range of 30 to 150 mgKOH/g is preferable, and a range of 40 to 120 mgKOH/g is more preferable, since a curable composition can be obtained. In the present disclosure, the acid value of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group is a value measured by the neutralization titration method of JIS K 0070 (1992).

<Amidoimide resin (B4) having an acid group and a polymerizable unsaturated group>
In the present embodiment, the amideimide resin (B4) having an acid group and a polymerizable unsaturated group includes, for example, an amideimide resin (b4-1) having an acid group and/or an acid anhydride group, and an amideimide resin (b4-1) having a hydroxyl group (meth ) an acrylate compound (b1-5) and/or a (meth)acrylate compound having an epoxy group, and optionally a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and 1 selected from the group consisting of an acid anhydride group Examples include those obtained by reacting compounds having at least one reactive functional group. The compound having a reactive functional group may or may not have a (meth)acryloyl group.
The amide imide resin (b4-1) having an acid group and/or an acid anhydride group may have either an acid group or an acid anhydride group, or both. The amideimide resin (b4-1) has an acid anhydride group from the viewpoint of reactivity and reaction control with the (meth)acrylate compound (1-5) having a hydroxyl group or an epoxy compound having a (meth)acryloyl group. and more preferably have both an acid group and an acid anhydride group. The solid content acid value of the amideimide resin (b4-1) is preferably in the range of 60 to 350 mgKOH/g as measured under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value under the condition that the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mgKOH/g.

In addition to the polyisocyanate compound (b1-4) and the polybasic acid anhydride (b1-3), the amide imide resin (b4-1) can also be used in combination with a polybasic acid as a reaction raw material, if necessary. .
Any compound having two or more carboxyl groups in one molecule can be used as the polybasic acid. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro phthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. be done. As the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used.
The above polybasic acids can be used alone or in combination of two or more.

As the (meth)acrylate compound having an epoxy group, other specific structures are not particularly limited as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. can. For example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, glycidyl group-containing (meth)acrylate monomers such as epoxycyclohexylmethyl (meth)acrylate, hydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether , biphenol diglycidyl ether, and mono(meth)acrylated products of diglycidyl ether compounds of bisphenol diglycidyl ether.
The epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

Further, the specific structure or production method of the amideimide resin (b4-1) having an acid group and/or an acid anhydride group is not particularly limited, and general amideimide resins and the like can be widely used. The amide imide resin (b4-1) of the present embodiment is preferably obtained by reacting, for example, a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3).
Further, in the present embodiment, as the polyisocyanate compound (b1-4), since a resin composition having an acid group and a polymerizable unsaturated group having high solvent solubility is obtained, an alicyclic diisocyanate compound or its Modified products, aliphatic diisocyanate compounds or modified products thereof are preferred, and alicyclic diisocyanates or modified isocyanurate compounds thereof, aliphatic diisocyanates or modified isocyanurate compounds thereof are more preferred.
In the present embodiment, in the total mass of the polyisocyanate compound (b1-4), the ratio of the total mass of the alicyclic diisocyanate compound or modified product thereof and the aliphatic diisocyanate compound or modified product thereof is 70% by mass or more. It is preferable that the content is 90% by mass or more.
Further, when the alicyclic diisocyanate compound or its modified form and the aliphatic diisocyanate compound or its modified form are used in combination, the mass ratio of both (alicyclic diisocyanate compound or its modified form/aliphatic diisocyanate compound or its modified form) is preferably in the range of 30/70 to 70/30.

The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in the present embodiment is not particularly limited, and any method may be used. The production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary.
As the basic catalyst, the same basic catalyst as described in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used. Using independently can also use 2 or more types together.
As the organic solvent, the same organic solvent as described in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used. can also be used in combination of two or more.

In the present embodiment, the amideimide resin (B4) having an acid group and a polymerizable unsaturated group may be an amideimide resin (b4-1) having an acid group and/or an acid anhydride group, depending on the desired resin performance. In addition to the hydroxyl group-containing (meth)acrylate compound (b1-5) and/or the epoxy group-containing (meth)acrylate compound (b4-2), other reaction raw materials may be used in combination. In this case, the ratio of the total mass of the components (b4-1) to (b4-2) in the total mass of the reaction raw materials of the resin (B4) having an acid group and a polymerizable unsaturated group is 80% by mass or more. is preferred, and 90% by mass or more is more preferred.

The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in the present embodiment is not particularly limited, and any method may be used. For example, all reaction raw materials containing an amide imide resin (b4-1), a hydroxyl group-containing (meth)acrylate compound (b1-5) and/or an epoxy group-containing (meth)acrylate compound (b4-2) are reacted together. It may be produced by a method in which the reaction raw materials are reacted sequentially. Further, for example, the reaction between the amide imide resin (b4-1) and the hydroxyl group-containing (meth)acrylate compound (b1-5) is carried out by heating and stirring at a temperature of about 80 to 140° C. in the presence of a suitable basic catalyst. can be done by The production of the amide imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent if necessary, and if necessary a basic catalyst or an acidic catalyst may be used. .

The basic catalyst can be the same as the acidic catalyst and basic catalyst described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and they can be used alone. can also be used in combination of two or more.
Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. etc. A solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalysts can be used alone or in combination of two or more.

The acid value of the amideimide resin (B4) having an acid group and a polymerizable unsaturated group in the present embodiment is a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner. is preferably in the range of 30 to 150 mgKOH/g, more preferably in the range of 40 to 120 mgKOH/g. The acid value of the amideimide resin (B4) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS K 0070 (1992).

<Acrylamide resin (B5) having an acid group and a polymerizable unsaturated group>
The acrylamide resin (B5) having an acid group and a polymerizable unsaturated group of the present embodiment includes, for example, a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b ), an N-alkoxyalkyl (meth)acrylamide compound (b5-3), a polybasic acid anhydride (b1-3), and optionally an unsaturated monobasic acid (b1-2) as reaction raw materials, Examples thereof include resins obtained by reacting the reaction raw materials.

（上記一般式（８．１）～（８．５）中、Ｒ^８１～Ｒ^８４及びＲ^８７はそれぞれ独立して、炭素原子数１～２０のアルキル基、炭素原子数１～２０のアルコキシ基、アリール基又はハロゲン原子のいずれかを表し、Ｒ^８５及びＲ^８６はそれぞれ独立して、水素原子又はメチル基を表し、ｊ^８１～ｊ^８４及びｊ^８７はそれぞれ独立して、０又は１以上の整数を表し、好ましくは０又は１～３の整数であり、より好ましくは０又は１である。ｋ^８１～ｋ^８４及びｋ^８７はそれぞれ独立して、１以上の整数を表し、好ましくは、２又は３である。）
なお、上記一般式（８．１）～（８．５）における芳香環上の置換基の位置については、任意であり、例えば、一般式（８．２）のナフタレン環においてはいずれの環上の水素原子と置換していてもよく、一般式（８．３）では、ビフェニル１分子中に存在するベンゼン環のいずれの水素原子に置換していてもよく、一般式（８．４）では、アラルキル１分子中に存在するベンゼン環のいずれかの水素原子と置換していてもよく、一般式（８．５）では、アラルキル１分子中に存在するベンゼン環のいずれかの水素原子と置換していてもよいことを示し、１分子中における置換基の個数がｊ^８１～ｊ^８４及びｋ^８１～ｋ^８４であることを示している。

（上記一般式（９．１）～（９．５）中、ｈ^９１は、０又は１を表し、Ｒ^９１～Ｒ^９６はそれぞれ独立して、一価の脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基又はアラルキル基のいずれかを表し、ｋ^９１～ｋ^９６はそれぞれ独立して、０又は１～４の整数を表し、Ｚ^９１～Ｚ^９６はそれぞれ独立して、ビニル基、ハロメチル基、ヒドロキシメチル基又はアルキルオキシメチル基のいずれかを表し、Ｙ^９１は、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子又はカルボニル基のいずれかを表し、ｎ^９１は１～４の整数を表す。）
上記一般式（９．１）～（９．５）で表される化合物は、単独で用いることも２種以上を併用することもできる。 In the present embodiment, the phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the phenolic hydroxyl group-containing compound (b5-1) include compounds represented by any of the following general formulas (8.1) to (8.5), aromatic polyhydroxy compounds (b5-4) and the following A reaction product with a compound represented by any of the general formulas (9.1) to (9.5) as an essential reaction raw material, or an aromatic polyhydroxy compound (b5-4) or other phenol in the molecule A novolac-type phenolic resin containing one or more of the compounds (b5-5) having one hydroxyl group as a reaction raw material can also be used.

(In general formulas (8.1) to (8.5) above, R ⁸¹ to R ⁸⁴ and R ⁸⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, , an aryl group or a halogen atom, R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom or a methyl group, j ⁸¹ to j ⁸⁴ and j ⁸⁷ each independently represent 0 or 1 or more represents an integer, preferably 0 or an integer of 1 to 3, more preferably 0 or 1. k ⁸¹ to k ⁸⁴ and k ⁸⁷ each independently represent an integer of 1 or more, preferably 2 or 3.)
The position of the substituent on the aromatic ring in the general formulas (8.1) to (8.5) is arbitrary. For example, in the naphthalene ring of the general formula (8.2), In general formula (8.3), any hydrogen atom of a benzene ring present in one molecule of biphenyl may be substituted, and in general formula (8.4) , may be substituted with any hydrogen atom of a benzene ring present in one aralkyl molecule, and in the general formula (8.5), substituted with any hydrogen atom of a benzene ring present in one aralkyl molecule It indicates that the number of substituents in one molecule is j ⁸¹ to j ⁸⁴ and k ⁸¹ to k ⁸⁴ .

(In general formulas (9.1) to (9.5) above, h ⁹¹ represents 0 or 1, R ⁹¹ to R ⁹⁶ each independently represent a monovalent aliphatic hydrocarbon group, an alkoxy group, represents a halogen atom, an aryl group, an aryloxy group or an aralkyl group, k ⁹¹ to k ⁹⁶ each independently represent an integer of 0 or 1 to 4, Z ⁹¹ to Z ⁹⁶ each independently represents either a vinyl group, a halomethyl group, a hydroxymethyl group or an alkyloxymethyl group, Y ⁹¹ represents any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl group, n ⁹¹ represents an integer from 1 to 4.)
The compounds represented by the general formulas (9.1) to (9.5) can be used alone or in combination of two or more.

Examples of aromatic polyhydroxy compounds (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, In addition to tetrahydroxybiphenyl, bisphenol and the like, compounds having one or more substituents on their aromatic nuclei are also included. Examples of substituents on the aromatic nucleus include methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group and the like. monovalent aliphatic hydrocarbon group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; fluorine atom, chlorine atom, halogen atom such as bromine atom; phenyl group, naphthyl group, anthryl group, and The aliphatic hydrocarbon group, the alkoxy group, the aryl group substituted with a halogen atom or the like on these aromatic nuclei; a phenyloxy group, a naphthyloxy group; An alkoxy group, an aryloxy group substituted with a halogen atom, etc.; An aralkyl group substituted with an atom or the like can be mentioned. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, a halogen-free compound is preferable because a resin having an acid group and a polymerizable unsaturated group with high insulation reliability can be obtained.

Examples of the novolak-type phenolic resin include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.

The other compound (b5-5) having one phenolic hydroxyl group in the molecule may be any aromatic compound having one hydroxyl group on the aromatic nucleus, such as phenol or the aromatic nucleus of phenol. Phenolic compounds having one or more substituents thereon, naphthol compounds having one or more substituents on the naphthol or naphthol aromatic nucleus, anthracenol or one or more on the anthracenol aromatic nucleus and an anthracenol compound having a substituent of. Examples of substituents on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, etc. Specific examples of each are as described above. is. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, penthylaldehyde, hexylaldehyde; salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4 -hydroxybenzaldehyde such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 - benzaldehydes having both hydroxy and alkoxy groups such as ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, hydroxynaphthaldehyde such as 2-hydroxy-1-naphthaldehyde and 6-hydroxy-2-naphthaldehyde; halogenated benzaldehyde such as brombenzaldehyde;

Examples of the alkylene carbonate (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate and the like. Among these, ethylene carbonate or propylene carbonate is preferable because a curable composition capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner can be obtained. The alkylene carbonates can be used alone or in combination of two or more.

Examples of the alkylene oxide (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide and the like. Among these, ethylene oxide or propylene oxide is preferable because a curable composition capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner can be obtained. The alkylene oxides can be used alone or in combination of two or more.

Examples of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl (Meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide and the like. Among these, N-methoxymethyl(meth)acrylamide is preferred because it provides a resin composition capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner.
The N-alkoxyalkyl(meth)acrylamide compounds (b5-3) can be used alone or in combination of two or more.

In the present embodiment, when the N-alkoxyalkyl(meth)acrylamide compound (b5-3) is used as a reaction raw material for the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, the N-alkoxyalkyl(meth)acrylamide The equivalent ratio [(b5-3)/(b1-3)] of the compound (b5-3) and the polybasic anhydride (b1-3) improves elongation, adhesion and low dielectric properties in a well-balanced manner. It is preferably in the range of 0.2 to 7, more preferably in the range of 0.25 to 6.7, since a curable composition capable of forming a cured product that can be cured can be obtained.

［上記式（１０．１）又は（１０．２）中、Ｒ^ｂ２及びＲ^ｂ８はそれぞれ独立して、水素原子又は炭素原子数１～４の一価の炭化水素基を表し、Ｒ^ｂ３及びＲ^ｂ９はそれぞれ独立して、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基又はハロゲン原子のいずれかを表し、ｎ^１及びｎ^２はそれぞれ独立して、１又は２を表し、Ｒ^ｂ４及びＲ^ｂ１０はそれぞれ独立して、メチレン基又は下記一般式（１１．１）～（１１．５）のいずれかで表される構造部位を表し、Ｒ^ｂ５及びＲ^ｂ６はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^ｂ５とＲ^ｂ６とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^ｂ１１は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^ｂ１２は、水素原子又はメチル基を表し、Ｒ^ｂ１及びＲ^ｂ７はそれぞれ独立して、前記Ｒ^ｂ３及び前記Ｒ^ｂ９で表される基、或いは、式（１０．１）で表される構造部位（Ｉ）又は式（１０．２）で表される構造部位（ＩＩ）が、＊印が付されたＲ^ｂ４又はＲ^ｂ１０を介して連結する結合点である。］

［上記一般式（１０．３）又は（１０．４）中、Ｒ^ｂ２及びＲ^ｂ８はそれぞれ独立して、水素原子又は炭素原子数１～４の炭化水素基を表し、Ｒ^ｂ３及びＲ^ｂ９はそれぞれ独立して、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基又はハロゲン原子のいずれかを表し、ｎ^３及びｎ^４はそれぞれ独立して、１又は２を表し、Ｒ^ｂ４及びＲ^ｂ１０はそれぞれ独立して、メチレン基又は下記式（１１．１）～（１１．５）のいずれかで表される構造部位を表し、Ｒ^ｂ５及びＲ^ｂ６はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^ｂ５とＲ^ｂ６とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^ｂ１１は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^ｂ１２は、水素原子又はメチル基を表し、Ｒ^ｂ１及びＲ^ｂ７はそれぞれ独立して、前記Ｒ^ｂ３及び前記Ｒ^ｂ９で表される基、或いは、一般式（１０．３）で表される構造部位（ＩＩＩ）又は一般式（１０．４）で表される構造部位（ＩＶ）が、＊印が付されたＲ^ｂ４又はＲ^ｂ１０を介して連結する結合点である。］

［上記一般式（１１．１）～（１１．５）中、ｈ^９１は、０又は１を表し、Ｒ^９１～Ｒ^９６はそれぞれ独立して、一価の脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基又はアラルキル基のいずれかを表し、ｎ^９１～ｎ^９６はそれぞれ独立して、０又は１～４の整数を表し、Ｙ^９１は、炭素原子数１～４のアルキレン基、酸素原子、硫黄原子又はカルボニル基のいずれかを表し、ｎ^９１は１～４の整数を表し、Ｒ^１１１～Ｒ^１１６はそれぞれ独立して、水素原子又はメチル基を表し、Ｗは、下記式（１２．１）又は（１２．２）を表す。］

［上記式（１２．１）又は（１２．２）中、Ｒ^１２１及びＲ^１２４はそれぞれ独立して、水素原子又は炭素原子数１～４の炭化水素基を表し、Ｒ^１２２及びＲ^１２３はそれぞれ独立して、水素原子又は炭素原子数１～２０の炭化水素基を表し、但し、Ｒ^１２２とＲ^１２３とが、連結して飽和又は不飽和の環を形成してもよく、Ｒ^１２５は、炭素原子数１～１２の二価の炭化水素基を表し、Ｒ^１２６は、水素原子又はメチル基を表す。］ In the present embodiment, the method for producing the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all of the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the phenolic hydroxyl group-containing compound (b5-1) is first reacted with an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b) (for example, reaction in the presence of a basic catalyst in the temperature range of 100 to 200° C.), then unsaturated monobasic acid (b1-2) and/or N-alkoxyalkyl (meth)acrylamide compound (b2-3b). (for example, reaction in the presence of an acidic catalyst in a temperature range of 80 to 140° C.), and then polybasic acid anhydride (b1-3) is reacted (for example, reaction in a temperature range of 80 to 140° C.). A method is preferred.
The acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in the present embodiment is a resin obtained from the reaction raw materials described above. For example, the acrylamide resin (B5) has a structure in which the structural site (I) represented by the following general formula (10.1) and the structural site (II) represented by the following general formula (10.2) are repeated. A resin having a resin structure as a unit, or a structural moiety (III) represented by the following formula (10.3) and a structural moiety (IV) represented by the following formula (10.4) are used as repeating structural units. A resin having a resin structure is mentioned.

[In the above formula (10.1) or (10.2), R ^b2 and R ^b8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ^b3 and R ^b9 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom; n ¹ and n ² each independently 1 or 2, R ^b4 and R ^b10 each independently represent a methylene group or a structural moiety represented by any of the following general formulas (11.1) to (11.5), R ^b5 and R ^b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ^b5 and R ^b6 may be linked to form a saturated or unsaturated ring; ^b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ^b12 represents a hydrogen atom or a methyl group, R ^b1 and R ^b7 each independently represent R ^b3 and R ^b9 ; or the structural moiety (I) represented by formula (10.1) or the structural moiety (II) represented by formula (10.2) is marked with an asterisk R ^b4 or R It is a connection point that connects via ^b10 . ]

[In the above general formula (10.3) or (10.4), R ^b2 and R ^b8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ^b3 and R ^b9 are each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom; n ³ and n ⁴ each independently represent 1 or 2, R ^b4 and R ^b10 each independently represent a methylene group or a structural moiety represented by any of the following formulas (11.1) to (11.5), and R ^b5 and R ^b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ^{b5 and} R ^b6 may be linked to form a saturated or unsaturated ring; represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ^b12 represents a hydrogen atom or a methyl group, R ^b1 and R ^b7 are each independently represented by R ^b3 and R ^b9 group, or the structural moiety (III) represented by the general formula (10.3) or the structural moiety (IV) represented by the general formula (10.4) is R ^b4 or R ^b10 marked with * is a connection point that connects via ]

[In the above general formulas (11.1) to (11.5), h ⁹¹ represents 0 or 1, R ⁹¹ to R ⁹⁶ each independently represent a monovalent aliphatic hydrocarbon group, an alkoxy group, represents either a halogen atom, an aryl group or an aralkyl group, n ⁹¹ to n ⁹⁶ each independently represents an integer of 0 or 1 to 4, Y ⁹¹ is an alkylene group having 1 to 4 carbon atoms, oxygen represents either an atom, a sulfur atom or a carbonyl group, n ⁹¹ represents an integer of 1 to 4, R ¹¹¹ to R ¹¹⁶ each independently represents a hydrogen atom or a methyl group, W represents the following formula (12 .1) or (12.2). ]

[In the above formula (12.1) or (12.2), R ¹²¹ and R ¹²⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ¹²² and R ¹²³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R ¹²² and R ¹²³ may combine to form a saturated or unsaturated ring, and R ¹²⁵ is represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹²⁶ represents a hydrogen atom or a methyl group; ]

The acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in the present embodiment is a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner. is preferably in the range of 30 to 150 mgKOH/g, more preferably in the range of 40 to 120 mgKOH/g. The acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured based on the neutralization titration method of JIS K 0070 (1992).

<Ester Resin (B6) Having Acid Group and Polymerizable Unsaturated Group>
Examples of the ester resin (B6) having an acid group and a polymerizable unsaturated group in the present embodiment include a phenolic hydroxyl group-containing compound (b5-1), an alkylene oxide (b5-2b) or an alkylene carbonate (b5-2a ), an unsaturated monobasic acid (b1-2), and a resin obtained by reacting a polybasic acid anhydride (b1-3).

As the alkylene oxide (b5-2b), the same alkylene oxide (b5-2b) as exemplified above can be used. Among these, ethylene oxide and propylene oxide are preferable because they yield a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner.
Alkylene oxide (b5-2b) can be used alone or in combination of two or more.

As the alkylene carbonate (b5-2a), the same alkylene carbonate (b5-2a) as exemplified above can be used. Among these, ethylene carbonate or propylene carbonate is preferable because a curable composition capable of forming a cured product capable of improving elongation, adhesion and low dielectric properties in a well-balanced manner can be obtained.
Alkylene carbonate (b5-2a) can be used alone or in combination of two or more.

The method for producing the ester resin (B6) having an acid group and a polymerizable unsaturated group of the present embodiment is not particularly limited, and any method may be used. The production of the ester resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent if necessary, and if necessary, a basic catalyst and an acidic catalyst may be used.

As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more. As the basic catalyst, the same basic catalyst as exemplified above can be used, and the basic catalyst can be used alone or in combination of two or more. As the acidic catalyst, the same ones as those exemplified as the acidic catalysts described above can be used, and the acidic catalysts can be used alone or in combination of two or more.
The above are the contents of the essential components contained in the resin composition having the resin having an acid group and a polymerizable unsaturated group and the phosphorus-containing active ester in the present embodiment.

(Optional additive component)
In addition to the compounds or resins described above, the resin composition in the present embodiment can also contain various known additives such as ultraviolet stabilizers and storage stabilizers.

The method for producing the resin composition of the present embodiment is not particularly limited, and the resin composition can be produced by kneading the various components described above using a kneader such as rolls.

[Curable composition]
The curable composition in the present embodiment preferably contains the resin composition described above and a photopolymerization initiator. More specifically, the preferred curable composition of the present embodiment comprises the above-described resin composition (essentially containing a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group), and photopolymerization initiation agent, and if necessary, a curing agent, a solvent, other resins, and additives.
Examples of the curing agent include epoxy resins and curing agents other than the epoxy resin (hereinafter referred to as other curing agents). Further, examples of the other resins include resins other than resins having phosphorus-containing active esters and acid groups and polymerizable unsaturated groups. Furthermore, examples of the additives include fillers, flame retardants, curing accelerators, antioxidants, and UV inhibitors.

In the curable composition of the present embodiment, the content of the phosphorus-containing active ester compound is preferably in the range of 5 to 95% by mass, more preferably 20 to 80% by mass, in the solid content of the curable composition. .
In the curable composition of the present embodiment, the content of the resin having an acid group and a polymerizable unsaturated group is preferably in the range of 5 to 95% by mass in the solid content of the curable composition, and 20 to 80 A weight percent range is more preferred.

In the curable composition of the present embodiment, the content of the resin composition described above is preferably 10 to 95% by mass, relative to the total amount (100% by mass) of the curable composition, and 20 to 80% by mass. % is more preferable.
In the curable composition of the present embodiment, the content of the curing agent is preferably 0 to 50% by mass, and 5 to 40% by mass, relative to the total amount (100% by mass) of the curable composition. is more preferable.
In the curable composition of the present embodiment, the content of the additive is preferably 0 to 10% by mass, relative to the total amount (100% by mass) of the curable composition, and 0.1 to 5% by mass. is more preferable.
Hereinafter, the photopolymerization initiator, curing agent, solvent, other resins and additives, which are components that can be contained in the curable composition of the present embodiment, will be described in detail.

(Photoinitiator)
A suitable photopolymerization initiator can be selected and used depending on the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Also, the photopolymerization initiator is preferably a radical polymerization initiator. Specific examples of such photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 1,2-(dimethylamino )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl - acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds;
Furthermore, specific examples of photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl -1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2 ,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and the like.
In addition, commercially available photopolymerization initiators that can be used in the present embodiment include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", and "Omnirad-369". , "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100","Omnirad-754","Omnirad-784","Omnirad-500","Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI ”, “Kayacure-EPA”, “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Vicure-10”, “Vicure-55” (manufactured by Stouffer Chemical), “Trigonal P1” (manufactured by Akzo) , "Sundray 1000" (manufactured by Sands), "Deep" (manufactured by Upjohn), "Quanta Cure-PDO", "Quanta Cure-ITX", "Quanta Cure-EPD" (manufactured by Ward Blenkinsop), " Runtechure-1104” (manufactured by Runtec) and the like.

The content of the photopolymerization initiator in the curable composition of the present embodiment is 0.1 parts by mass or more with respect to a total of 100 parts by mass of the resin having a phosphorus-containing active ester compound and an acid group and a polymerizable unsaturated group. It is preferably 10 parts by mass or less.

(Other various additives)
The curable composition of the present embodiment may optionally include a curing agent, a curing accelerator, other resins, organic solvents, flame retardants, fillers, pigments, antifoaming agents, and viscosity adjusting agents within the scope of the purpose. Appropriate amounts of various additives such as agents, leveling agents, and storage stabilizers can also be contained.

(curing agent)
Examples of the curing agent of the present embodiment include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), and epoxy resins are preferred.

<Epoxy resin>
Epoxy resins, which are suitable curing agents in the present embodiment, are not particularly limited. For example, a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups. is preferably
The epoxy resin of the present embodiment is not particularly limited, but phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl novolac epoxy resins such as novolak epoxy resins;
Aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins;
Bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as tetrabromobisphenol A type epoxy resin;
Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton;
Naphthalene type epoxy resin;
Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin;
Dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin;
Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins, triglycidyl-p-aminophenol type epoxy resins, diaminodiphenylsulfone glycidylamine type epoxy resins;
diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins;
Examples include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.
Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing phenolic compounds are preferred. is more preferable from the viewpoint of The epoxy resins described above may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin of the present embodiment is preferably 120-400 g/eq, more preferably 150-300 g/eq. When the epoxy equivalent of the epoxy resin is 120 g/eq or more, it is preferable because the dielectric properties of the resulting cured product are excellent. It is preferable because it has an excellent balance of low dielectric properties.

The softening point of the epoxy resin of the present embodiment is preferably 20 to 200° C., more preferably 40 to 150° C., from the viewpoint of improving elongation, adhesion and low dielectric properties in a well-balanced manner.

In the present embodiment, with respect to the amount of epoxy resin used, the ester group in the phosphorus-containing active ester and the acid group in the resin (B) having an acid group and a polymerizable unsaturated group are used as (total) functional groups. Sometimes, the functional group equivalent ratio of the amount of epoxy resin used ((phosphorus-containing active ester + resin (B) having an acid group and a polymerizable unsaturated group)/epoxy resin) is 0.2 to 2. More preferably, it is 0.4 to 1.5. When the functional group equivalent ratio is 0.2 or more, it can be a curable composition capable of forming a cured product that can improve the elongation, adhesion and low dielectric properties of the obtained cured product in a well-balanced manner. preferable. When the functional group equivalent ratio exceeds 2, heat resistance and curability are lowered, so it is preferable to use within the above range.

(Other curing agents)
The curable composition of this embodiment may contain other curing agents along with or in place of the epoxy resin. Examples of other curing agents include, but are not limited to, amine curing agents, acid anhydride curing agents, phenolic resin curing agents, and the like.
The amine curing agent is not particularly limited, but diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethyl Aliphatic amines such as piperazine, mencenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl and aromatic amines such as aminomethyl)phenol.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tri trimellitate, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexenedicarboxylic anhydride.

Examples of the phenol resin curing agent include phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak resin, biphenyl novolak resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, and triphenolmethane type resin. , tetraphenol ethane type resin, aminotriazine-modified phenol resin, and the like.
Any of the other curing agents mentioned above may be used alone or in combination of two or more.

In the present embodiment, regarding the amount of other curing agents (amine curing agent, acid anhydride curing agent, phenolic resin curing agent) used, the ester group in the phosphorus-containing active ester, and the acid group and the polymerizable unsaturated group are When the acid groups in the resin (B) having (total) functional groups, the functional group equivalent ratio of the amount of the other curing agent used ((phosphorus-containing active ester + acid group and polymerizable unsaturated group The resin (B))/other curing agent) is more preferably 0.2 to 2, more preferably 0.4 to 1.5. When the functional group equivalent ratio is 0.2 or more, the elongation, adhesion and low dielectric properties of the resulting cured product can be improved in a well-balanced manner, which is preferable. If the functional group equivalent ratio exceeds 2, the curability is lowered, so it is preferable to use it within the above range.

<Curing accelerator>
The curing accelerator is not particularly limited, but includes phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, and the like. The above curing accelerators may be used singly or in combination of two or more.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripparatolylphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5, 4,0]-undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN) and the like.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2 -methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.

Examples of the urea curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea and the like.
Among the curing accelerators mentioned above, 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP) are preferably used.

The content of the curing accelerator in the curable composition of the present embodiment can be appropriately adjusted in order to obtain the desired curability. It is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass. When the content of the curing accelerator is 0.01 parts by mass or more, the curability is excellent, which is preferable. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, the insulation reliability is excellent, which is preferable. From the same point of view, the content of the curing accelerator is 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. is more preferable, and 3 parts by mass or less is more preferable.

(other resin)
The curable composition of this embodiment may contain other resins in addition to or instead of the epoxy resin or other curing agent.
Specific examples of the other resins are not particularly limited, but maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate esters. Examples thereof include resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphates, and phosphate-carbonate copolymers. These other resins may be used alone or in combination of two or more.
The content of other resins in the curable composition of the present embodiment is preferably 50% by mass or less of the total.

(solvent)
The curable composition of this embodiment may be prepared without a solvent, or may contain a solvent. The solvent has a function of adjusting the viscosity of the curable composition.
Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.
The content of the solvent in the curable composition of the present embodiment is preferably 0 to 90% by mass in the total amount (100% by mass) of the curable composition, more preferably 10 to 90% by mass. , more preferably 20 to 80% by mass. It is preferable that the content of the solvent is 10% by mass or more because the handleability is excellent. On the other hand, a solvent content of 90% by mass or less is preferable from the viewpoint of economy.

(Additive)
The curable composition of this embodiment may contain additives. Examples of the additive include the curing accelerator, flame retardant, filler, and the like.

<Flame retardant>
The flame retardant of the present embodiment is not particularly limited, but includes inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like.
Examples of the inorganic phosphorus-based flame retardant include, but are not limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphate amides.

The organic phosphorus flame retardant is not particularly limited, but methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphate esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphine Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 Cyclic phosphorus compounds such as -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; Examples include compounds obtained by reacting with aldehyde compounds and phenol compounds.
The halogen-based flame retardant is not particularly limited, but brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2, -bis(tetrabromophthalimide), 2, 4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid and the like. The above flame retardants may be used alone or in combination of two or more.

The content of the flame retardant of the present embodiment is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. It is preferably from 1 to 30 parts by mass. It is preferable that the content of the flame retardant is 0.1 parts by mass or more because flame retardancy can be imparted. On the other hand, when the content of the flame retardant is 50 parts by mass or less, it is preferable because flame retardancy can be imparted while maintaining dielectric properties. From the same viewpoint, the content of the flame retardant is more preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. , and more preferably 30 parts by mass or less.

(filler)
Examples of fillers in this embodiment include organic fillers and inorganic fillers. The organic filler has a function of improving elongation, a function of improving mechanical strength, and the like. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and imparting flame retardancy.
Examples of the organic filler include, but are not particularly limited to, polyamide particles.
The inorganic filler is not particularly limited, but silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitride Boron, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate , calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Among these, it is preferable to use silica. At this time, as silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like can be used.

Moreover, the said filler may be surface-treated as needed. At this time, the surface treatment agent that can be used is not particularly limited, but aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based cups. A ring agent or the like may be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldimethoxysilane, silazane and the like. In addition, the above fillers may be used alone or in combination of two or more.

The content of the filler of the present embodiment is 0.5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. Preferably, it is 5 to 80 parts by mass. When the content of the filler is 0.5 parts by mass or more, it is preferable because the effect of the filler can be sufficiently imparted. On the other hand, the content of the filler is preferably 95 parts by mass or less so as not to increase the viscosity of the compound and impair the moldability. From the same point of view, the content of the filler is more preferably 5 parts by mass or more with respect to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. , and more preferably 80 parts by mass or less.
The method for producing the curable composition of the present embodiment is not particularly limited, and the composition can be produced by kneading the various components described above using a kneader such as rolls.

[Cured product]
The cured product in this embodiment is obtained by curing the curable composition described above. Since the phosphorus-containing active ester itself contained in the curable composition has a low dielectric loss tangent, the cured product obtained from the curable composition also has a low dielectric loss tangent, and the obtained cured product has flexibility, Adhesion to metals such as copper foil due to flexibility and low dielectric properties can be expressed, which is a preferred embodiment.
The cured product of the present embodiment can be obtained by irradiating the curable composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

In this embodiment, an ultraviolet lamp is generally used as the ultraviolet light source from the viewpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
The integrated amount of active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ/m ² , more preferably 0.5 to 10 kJ/m ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed. The irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.

Further, in the present embodiment, as another method of obtaining a cured product obtained by subjecting the curable composition to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is 100 to 300 ° C. , The heating time is preferably 1 to 24 hours.

Applications in which the curable composition or cured product of the present embodiment is used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, and circuit board applications such as build-up adhesive films. Insulating materials, resist materials, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, molded products made by curing the above composite materials etc. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive film applications for build-ups are used for so-called electronic component built-in substrates in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. can be used as an insulating material for Furthermore, among the above, the curable composition of the present disclosure is a semiconductor sealing material, a resist material, taking advantage of the characteristics that the cured product has excellent flexibility, adhesion, low dielectric properties, and heat resistance. It is preferably used for semiconductor devices, prepregs, flexible wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and moldings obtained by curing the above composite materials.

[Insulating material]
The insulating material in this embodiment consists of the curable composition described above. Preferably, the insulating material of the present embodiment is obtained by irradiating the curable composition described above with an active energy ray to cure it. The insulating material of this embodiment is excellent in elongation, adhesion, and low dielectric properties. Examples of the insulating material include the above-described interlayer insulating material for buildup boards, insulating material for circuit boards such as buildup adhesive film, insulating material for circuit boards, and insulating material for electronic component built-in boards. For example, as a method for producing a build-up substrate from the curable composition, there is a method comprising the following three steps. The first step is a step of applying the above-mentioned curable composition appropriately blended with rubber, filler, etc. to a circuit board having a circuit formed thereon by using a spray coating method, a curtain coating method, or the like, and then curing the composition. In step 2, after drilling a predetermined through-hole portion or the like as necessary, the surface is treated with a roughening agent, and the surface is washed with hot water to form unevenness, and a metal such as copper is removed. This is a plating process, and the third process is a process of sequentially repeating such operations as desired to alternately build up resin insulating layers and conductor layers of a predetermined circuit pattern. It should be noted that it is preferable to form the through-hole portion after forming the outermost resin insulating layer. The first step can also be carried out by laminating a build-up film that has been previously coated to a desired thickness and dried, in addition to the solution application method described above. In addition, the build-up board of the present disclosure is obtained by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil to a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to manufacture a build-up substrate by omitting the steps of forming a hardened surface and plating.

[Resist material]
The resist member in this embodiment is made of the curable composition described above. The resist member is formed, for example, by applying the curable composition on a substrate, volatilizing and drying the organic solvent in a temperature range of about 60 to 100 ° C., and then applying active energy through a photomask on which a desired pattern is formed. It can be obtained by exposing to a line, developing an unexposed area with an alkaline aqueous solution, and further curing by heating at a temperature range of about 140 to 180°C. The resist member of this embodiment is excellent in low dielectric properties and elongation.

EXAMPLES The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples. In the following, "parts" and "%" are based on mass unless otherwise specified. GPC measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, and FD-MS spectrum measurement were carried out under the following conditions.

(Evaluation method)
<GPC measurement>
Measurements were performed using the following measurement apparatus and measurement conditions, and GPC charts of diphenyl isophthalate derivatives, phenolic hydroxyl group-containing resins, and active esters obtained in Synthesis Examples and Examples shown below were obtained. From the results of the GPC chart, the target product (diphenyl isophthalate derivative (a'), phosphorus-containing active ester, and resin (B) having an acid group and a polymerizable unsaturated group) was generated.
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation
Column: guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + Tosoh Corporation Made by "TSK-GEL G4000HXL"
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used according to the measurement manual of the "GPC Workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of solid content of diphenyl isophthalate derivative (a') and phosphorus-containing active ester obtained in the Synthesis Examples and Examples shown below was filtered through a microfilter. (50 μl) was used.

<FD-MS spectrum measurement>
FD-MS spectra were measured using the following measurement equipment and measurement conditions. From this result, a mass peak corresponding to the target product (active ester) having the repetition number p ¹¹ =1 was confirmed.
Measuring device: JMS-T100GC AccuTOF
Measurement conditions Measurement range: m / z = 4.00 to 2000.00
Rate of change: 51.2mA/min
Final current value: 45mA
Cathode voltage: -10 kV
Recording interval: 0.07sec

< ¹ H-NMR measurement>
¹ H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE
Magnetic field strength: 600MHz
Number of times of accumulation: 32 times Solvent: DMSO-d6
Sample concentration: 30% by mass
From the results of the ¹ H-NMR chart, a peak derived from the target product was confirmed, confirming that the target product was obtained in each reaction.
< ¹³ C-NMR measurement>
¹³ C-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE
Magnetic field strength: 150MHz
Number of times of accumulation: 320 times Solvent: DMSO-d6
Sample concentration: 30% by mass
From the results of the ¹³ C-NMR chart, a peak derived from the target product was confirmed, confirming that the target product was obtained in each reaction.

<Theoretical phosphorus content>
Theoretical phosphorus content (%) = 100 × [charge amount of phosphorus-containing raw material (parts by mass) × (phosphorus content of phosphorus-containing raw material (mass%) / 100)] / (phosphorus synthesized using phosphorus-containing raw material Theoretical yield of the compound contained)
As for the phosphorus content of the phosphorus-containing raw material, the product catalog value was used when a product was used.
The phosphorus-containing compound refers to the phosphorus-containing polyhydric alcohol compound (C), phosphorus-containing active ester, and phosphorus-containing intermediate product (b') used in Examples and Comparative Examples.

[Method for measuring elongation]
Elongation measurements were based on tensile tests. Specifically, the same test piece 1 (cured product) as described in the following [Evaluation method for adhesion] column was cut into a size of 10 mm × 80 mm, and a precision universal testing machine Autograph “AG” manufactured by Shimadzu Corporation -IS”, a tensile test was performed on the test piece 1 under the following measurement conditions. The elongation (%) until the test piece breaks was measured.
Measurement conditions: temperature 23° C., humidity 50%, distance between gauge lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm/min.

[Method of measuring dielectric constant]
The curable composition obtained in each example and comparative example was applied onto a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, after irradiating with ultraviolet rays of 10 kJ/m ² using a metal halide lamp, it was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece was stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and the dielectric constant of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

[Method of measuring dielectric loss tangent]
The curable composition obtained in each example and comparative example was applied to a glass substrate using an applicator so as to have a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, after irradiating with ultraviolet rays of 10 kJ/m ² using a metal halide lamp, it was heated at 160° C. for 1 hour to obtain a cured coating film. Then, the cured coating film was peeled off from the glass substrate to obtain a cured product. Next, a test piece was stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using "Network Analyzer E8362C" manufactured by Agilent Technologies. It was measured.

[Method for evaluating adhesion]
Adhesion was evaluated by measuring peel strength. Specifically, the curable compositions obtained in Examples and Comparative Examples were applied on a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) with a 50 μm applicator, and a metal halide lamp was used. After irradiating with ultraviolet rays of 10 kJ/m ² at a high temperature, it was heated at 160° C. for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product). This test piece 1 is cut into a size of 1 cm in width and 12 cm in length, and the 90° peel strength (N/cm) is measured using a peel tester ("A&D Tensilon" manufactured by A&D Co., Ltd., peel speed 50 mm/min). bottom. A larger value indicates better adhesion.

(Synthesis Example 1): Synthesis of Diphenyl Isophthalate Derivative (1) 864.0 parts by mass (8.0 mol) of o-cresol was added to a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. ) and 4,140.0 parts by mass of toluene were charged, and the system was replaced with nitrogen under reduced pressure to dissolve. Then, 808 parts by mass of isophthalic acid chloride (number of moles of acid chloride group: 4.0 mol) was charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, 2.07 parts by mass of tetrabutylammonium bromide is dissolved, and while purging with nitrogen gas, the inside of the system is controlled at 60° C. or less, and 1648.0 parts by mass of a 20% by mass sodium hydroxide aqueous solution is added dropwise over 3 hours. bottom. Stirring was then continued under the above conditions for 1.0 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by decanter dehydration to obtain a diphenyl isophthalate derivative (1). The GPC chart, ¹ H-NMR chart and FD-MS spectrum chart of the diphenyl isophthalate derivative (1) are shown in FIGS. 1 to 3, respectively.

(Synthesis Example 2): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) Phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ) 200.0 parts by mass, 156.4 parts by mass of propylene carbonate and tri 1.07 parts by mass of phenylphosphine (hereinafter referred to as TPP) was charged, heated to 190° C., and reacted until the reaction was completed to obtain a phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ). Also, it was confirmed that the hydroxyl group equivalent of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) was 253 g/eq. The GPC chart, ¹³ C-NMR chart and FD-MS spectrum chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) are shown in FIGS. 3 to 6, respectively.

(Synthesis Example 3): Synthesis of phosphorus-containing active ester (1) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with the diphenyl isophthalate derivative obtained in Synthesis Example 1 above ( 1) 137.0 g, 100.0 g of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2 above, and diazabicycloundecene (hereinafter abbreviated as "DBU") as a catalyst. ) and 0.24 parts by mass were charged, heated to 190° C., and reacted for 3 hours. Thereafter, the reaction was further carried out while o-cresol was removed by distillation under reduced pressure to obtain a phosphorus-containing active ester (1). The functional group equivalent weight of the obtained phosphorus-containing active ester (1) was 486 g/eq based on the charging ratio. The GPC chart, ¹³ C-NMR chart and FD-MS spectrum chart of the phosphorus-containing active ester (1) are shown in FIGS. 7 to 9, respectively.

(Synthesis Example 4): Synthesis of phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- was added to an eggplant flask equipped with a stirrer. 200 parts by mass of 10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ), 199.5 parts by mass of ethylene carbonate, and 0.96 parts by mass of TPP were charged at 180°C. A phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) was prepared by stirring until the reaction was completed. Also, it was confirmed that the hydroxyl group equivalent of the phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) was 227 g/eq. A GPC chart of the phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) is shown in FIG.

(Synthesis Example 5): Synthesis of phosphorus-containing active ester (2) 60.0 parts by mass of EC-HCA-HQ prepared in Synthesis Example 4 above instead of PC-HCA-HQ prepared in Synthesis Example 3 above Phosphorus-containing active ester (2) was synthesized in the same manner as in Synthesis Example 3, except that 91.7 parts by mass of diphenyl isophthalate derivative (1) and 0.15 parts by mass of DBU were used. The functional group equivalent weight of the obtained active ester (2) was 465 g/eq based on the charging ratio. A GPC chart of the phosphorus-containing active ester (2) is shown in FIG.

(Synthesis Example 6): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ)
10-[2-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd.) used in place of HCA-HQ used in Synthesis Example 4 above , trade name: HCA = NQ), 68.2 parts by mass of ethylene carbonate, and 0.50 parts by mass of DBU, the same procedure as in Synthesis Example 4 was performed to obtain a phosphorus-containing polyhydric alcohol compound (PC-HCA -NQ) were synthesized. Also, the hydroxyl equivalent of PC-HCA-NQ was 245 g/eq based on the charging ratio. A GPC chart of the contained polyhydric alcohol compound (PC-HCA-NQ) is shown in FIG.

(Synthesis Example 7): Synthesis of phosphorus-containing active ester (3) 71.5 parts by mass of PC-HCA-NQ synthesized in Synthesis Example 6 above instead of PC-HCA-HQ synthesized in Synthesis Example 3 above; Diphenyl isophthalate derivative (1) 100.9 parts by mass and DBU 0.34 parts by mass were used, and 0.17 parts by mass of 4-dimethylaminopyridine (hereinafter referred to as DMAP) was added in the same manner as in Synthesis Example 3. Operation was performed to synthesize a phosphorus-containing active ester (3). The functional group equivalent weight of the obtained phosphorus-containing active ester (3) was 484 g/eq based on the charging ratio. A GPC chart of the phosphorus-containing active ester (3) is shown in FIG.

(Synthesis Example 8): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-PPQ) Diphenylphosphinylhydroquinone (manufactured by Hokko Sangyo Co., Ltd., trade name: PPQ) used in place of HCA-HQ used in Synthesis Example 2 above (registered trademark)), 72.4 parts by mass of propylene carbonate, and 0.52 parts by mass of TPP. -PPQ) were synthesized. Also, it was confirmed that the hydroxyl equivalent of PC-PPQ was 208 g/eq. A GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-PPQ) is shown in FIG.

(Synthesis Example 9): Synthesis of phosphorus-containing active ester (4) 70.0 parts by mass of PC-PPQ synthesized in Synthesis Example 8 above, which was used instead of PC-HCA-HQ in Synthesis Example 3, and a diphenyl isophthalate derivative ( 1) Phosphorus-containing active ester (4) was synthesized in the same manner as in Synthesis Example 3, except that 116.5 parts by mass and 1.86 parts by mass of DBU were used. The functional group equivalent weight of the obtained phosphorus-containing active ester (4) was 447 g/eq based on the charging ratio. A GPC chart of the phosphorus-containing active ester (4) is shown in FIG.

(Synthesis Example 10): Production of Resin (1) Having Acid Groups and Polymerizable Unsaturated Groups In a flask equipped with a thermometer, a stirrer and a reflux condenser, 123 parts by mass of diethylene glycol monoethyl ether acetate was charged, followed by ortho Cresol novolak type epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86 ° C., epoxy equivalent: 214 g / eq) 214 parts by weight was dissolved, and 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts of methoquinone were dissolved. After adding 72 parts by mass of acrylic acid and 1.4 parts by mass of triphenylphosphine, the mixture was reacted at 120° C. for 10 hours while blowing air. Then, 72 parts by mass of diethylene glycol monoethyl ether acetate and 76 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110° C. for 3 hours to obtain Resin (1) having an acid group and a polymerizable unsaturated group. The resin (1) having an acid group and a polymerizable unsaturated group had a non-volatile content of 65% by mass and a solid content acid value of 80 mgKOH/g. The acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

(Synthesis Example 11): Production of Resin (2) Having Acid Groups and Polymerizable Unsaturated Groups In a flask equipped with a thermometer, a stirrer and a reflux condenser, 499.7 parts by mass of diethylene glycol monomethyl ether acetate was charged, Isocyanurate-modified isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, NCO% = 17.2%) 244.3 parts by mass and 192.0 parts by mass of trimellitic anhydride are dissolved, and dibutylhydroxytoluene is dissolved. 1.0 parts by mass was added. After reacting at 160° C. for 6 hours in a nitrogen atmosphere, it was confirmed that the NCO% was 0.1 or less. Then, after adding 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., hydroxyl value: 159.7 mgKOH / g) 147.6 parts by mass and 3.5 parts by mass of triphenylphosphine was added, and the reaction was carried out at 110° C. for 5 hours while blowing air. After that, 165.0 parts by mass of glycidyl methacrylate was added and reacted at 110° C. for 6 hours. Next, 110.4 parts by mass of succinic anhydride was added and reacted at 110° C. for 5 hours to obtain a resin (2) having an acid group and a polymerizable unsaturated group. The solid content acid value of the resin (2) was 80 mgKOH/g.

(Comparative Synthesis Example 1) Synthesis of Comparative Intermediate (1) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/ 330 parts by mass (equivalent weight, softening point 85° C.) and 1184 parts by mass of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Next, 101 parts by mass of isophthaloyl chloride was charged, and then 0.59 parts by mass of tetrabutylammonium bromide (hereinafter TBAB) was charged. 206 parts by mass of the aqueous solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration, and then toluene was removed by dehydration under reduced pressure to synthesize Comparative Intermediate (1). A GPC chart of the comparative intermediate (1) is shown in FIG.

(Comparative Synthesis Example 2) Synthesis of Phosphorus Atom-Containing Compound (1) In a flask equipped with a thermometer, a condenser, a fractionating tube, and a stirrer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 77.0 parts by mass of 10-oxide, 48.5 parts by mass of p-anisaldehyde, and 197.5 parts by mass of the comparative intermediate (1) were charged, heated to 90° C., and stirred while blowing nitrogen. . After that, the temperature was raised to 180° C. and stirred for 5 hours, and then the temperature was further raised to 190° C. and stirred for 9 hours. Water was removed from the reaction mixture by heating under reduced pressure to synthesize a phosphorus atom-containing compound (1). A GPC chart of the phosphorus atom-containing compound (1) is shown in FIG.

(Comparative Synthesis Example 3) Phosphorus Atom-Containing Ester Compound (1)
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 193.8 parts by mass of the phosphorus atom-containing compound (1) and 678.0 parts by mass of methyl isobutyl ketone. was replaced with nitrogen under reduced pressure and dissolved. Next, after charging 42.2 parts by mass of benzoic acid chloride, 0.56 parts by mass of TBAP was charged, and the inside of the system was controlled at 60°C or lower while purging with nitrogen gas. It dripped over time. Stirring was then continued under the above conditions for 1.0 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the methyl isobutyl ketone layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still to separate the layers, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. After that, water was removed by decanter dehydration, and then methyl isobutyl ketone was removed by vacuum dehydration to synthesize a phosphorus atom-containing ester compound (1). FIG. 18 shows a GPC chart of the phosphorus atom-containing ester compound (1).

(Example 1: Preparation of resin composition (1) and curable composition (1))
15 parts by mass of the phosphorus-containing active ester (1) obtained in Synthesis Example 3 and 62 parts by mass of the resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 11 are mixed to form a resin composition. (1) was prepared.
Further, 15 parts by mass of the phosphorus-containing active ester (1) obtained in Synthesis Example 3, 62 parts by mass of the resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 11, and ortho-cresol as a curing agent 19.9 parts by mass of a novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214), and 3.9 parts by mass of a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins), 0.4 parts by mass of 2-ethyl-4-methylimidazole and 0.3 parts by mass of 4-dimethylaminopyridine were mixed to obtain a curable composition (1).

(Examples 2 to 9: Preparation of resin composition and curable composition)
The phosphorus-containing active esters (1) to (4) obtained in the above synthesis examples and the resins (1) to (2) having an acid group and a polymerizable unsaturated group are mixed in the composition ratio shown in Table 1. Then, resin compositions (1) to (4) were prepared.

The resin compositions (1) to (4) obtained in the above examples, an ortho-cresol novolac type epoxy resin (manufactured by DIC Corporation "EPICLON N-680", epoxy equivalent: 214) as a curing agent, and a photopolymerizable Initiator ("Omnirad 907" manufactured by IGM Resins), 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine were mixed at the composition ratio shown in Table 1 to prepare curable compositions (1) to ( 9) was obtained. Then, various evaluations were performed on the curable compositions (1) to (9) in accordance with the procedure of the evaluation method described in the section (Evaluation method) above. The results are shown in Table 1 below.

(Comparative Examples 1 and 2: Preparation of composition)
In the same manner as in Examples 1 to 9, each component was mixed at the composition ratio shown in Table 1, and the compositions (C1) to (C2) and curable compositions (C1) to (C2) of Comparative Examples 1 and 2 were prepared. prepared. Then, various evaluations were performed on the curable compositions (C1) to (C2) of Comparative Examples 1 and 2. The results are shown in Table 1 below.

From the results in Table 1, it can be confirmed that when the resin compositions of Examples were used, cured products having excellent elongation, adhesion, and dielectric properties were obtained as compared with Comparative Examples.

According to the present disclosure, in the obtained cured product, using a resin composition excellent in elongation, adhesion, and dielectric properties, a curable composition containing the composition, and the curable composition The obtained resin composition, curable composition, cured product, insulating material, and resist member can be provided.

Claims (8)

Aromatic compounds having two or more carboxyl groups and/or acid halides or esters thereof (A), aromatic monoalcohols (B), phosphorus-containing polyhydric alcohol compounds (C) and ether bond-containing aliphatic compounds (D ) with a phosphorus-containing active ester as a reaction raw material,
A resin composition containing a resin having an acid group and a polymerizable unsaturated group. The phosphorus-containing active ester has the following general formula (J):

(In the above general formula (J), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and R ¹ and R ² are each independently derived from the ether bond-containing aliphatic compound (D) and Q ¹ and Q ² represent groups derived from the aromatic compound having two or more carboxyl groups and/or acid halides or esters thereof (A), and Ar ¹ and Ar ² are each independently represents a group derived from the aromatic monoalcohol (B), ^Ma represents a group represented by the following general formula (ii) or (iii),

[In the above general formula (ii) or (iii), R ³ each independently represents a group derived from the ether bond-containing aliphatic compound (D), Q ³ each independently represents the two or more carboxyl an aromatic compound having a group and/or an acid halide or ester thereof (A)-derived group, each Ar ³ independently represents a group derived from the aromatic monoalcohol (B), and x ² is , is the average number of iterations greater than or equal to 0.1, and y ² is the average number of iterations greater than or equal to 1. ]
^x1 is an average repetition number of 0.1 or more, ^y1 is an average repetition number of 1 or more, ^z1 is an average repetition number of 1 or more, and q represents 0 or 1. ), the resin composition according to claim 1. In the general formula (1), A is the following general formula (I):

[In general formula (I) above, M ¹ represents an aromatic group, R ³ and R ⁴ each independently represent a monovalent hydrocarbon group or a divalent hydrocarbon group, and R ³ or R ⁴ is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R ³ and R ⁴ are bonded together to form a cyclic structure, and * in the general formula (I) is , represents a bond that bonds with an oxygen atom. ] represents
R ¹ and R ² each independently represent a linear or branched alkylene group,
Q ¹ and Q ² represent a divalent aromatic group,
3. The resin composition of claim 2, wherein Ar ¹ and Ar ² each independently represent a monovalent aromatic group. The resin composition according to any one of claims 1 to 3, wherein the phosphorus content is 1.8% by mass or more relative to the total amount of the resin composition. A curable composition comprising the resin composition according to any one of claims 1 to 4 and a curing agent. A cured product obtained by curing the curable composition according to claim 5 . An insulating material comprising the curable composition according to claim 6 . A resist member comprising the curable composition according to claim 6 .

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