JP2023146886A - Resin composition, cured product, and article - Google Patents

Abstract

To provide a resin composition from which a cured coating film having excellent heat resistance and coating film appearance can be obtained.SOLUTION: A resin composition contains a maleimide resin (A) and a compound (B) having a polymerizable unsaturated group. The maleimide resin (A) contains a maleimide compound (a) having a specific first aromatic ring-maleimide skeleton and a specific second aromatic ring-maleimide skeleton in one molecule. The maleimide compound (a) is an asymmetric bismaleimide compound in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1-200 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a cured product, and an article.

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been used for inks, paints, coatings, adhesives, optical Widely used in the field of components, etc.

In particular, since the coating agent described above is required to have various properties including curability and heat resistance, it is important to manufacture it using an appropriate material that matches the above properties. In this regard, maleimide resin is one of the resins that tend to have excellent heat resistance in cured products, and there is room for consideration in applying the maleimide resin to the above-mentioned coating agent.

Conventionally, 4,4'-diphenylmethane bismaleimide type compounds are widely known as maleimide resins (see, for example, Patent Document 1).
Furthermore, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane type compounds are also known as maleimide resins with relatively high handling properties (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2-269716 Japanese Patent Application Publication No. 6-128225

However, when the above-mentioned 4,4'-diphenylmethane bismaleimide type maleimide resin is used in the above-mentioned coating agent, there is a problem that the appearance of the resulting cured coating film is poor due to turbidity occurring during compounding. there were. In addition, further improvement in heat resistance is also required.
Furthermore, the above-mentioned 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane-type maleimide resin did not meet recent market demands in terms of physical properties of the cured product, including heat resistance. .

Therefore, an object of the present invention is to provide a resin composition capable of obtaining a cured coating film having excellent heat resistance and coating appearance. Another object of the present invention is to provide a cured product obtained using the resin composition and an article using the cured product.

In order to solve the above problems, the present inventors have conducted intensive studies and found that a resin composition containing a specific maleimide resin and a compound having a polymerizable unsaturated group has excellent heat resistance and coating film. The present inventors have discovered that it is possible to improve the appearance, and have completed the present invention.

で示される第１の芳香環－マレイミド骨格と、下記一般式（２）：

で示される第２の芳香環－マレイミド骨格とを有するマレイミド化合物（ａ）を含む［ここで式（１）及び式（２）中、Ｒ^１～Ｒ^４は、それぞれ独立して、水素、メチル基又はエチル基を表し、Ａｒ^１及びＡｒ^２は、それぞれ独立して、１つ以上の置換基を有してもよい芳香環を表し、＊は、前記芳香環から他の部位への結合を表し、但し、Ａｒ^１及びＡｒ^２は、置換基の種類、置換基の数、及び置換基の位置の少なくともいずれかが互いに異なる］、ことを特徴とする、樹脂組成物である。 The resin composition of the present invention is a resin composition containing a maleimide resin (A) and a compound (B) having a polymerizable unsaturated group,
The maleimide resin (A) has the following general formula (1) in one molecule:

The first aromatic ring-maleimide skeleton represented by the following general formula (2):

A maleimide compound (a) having a second aromatic ring-maleimide skeleton represented by [where R ¹ to R ⁴ are each independently hydrogen or methyl] group or ethyl group, Ar ¹ and Ar ² each independently represent an aromatic ring which may have one or more substituents, and * represents a bond from the aromatic ring to another site. Ar ¹ and Ar ² are different from each other in at least one of the types of substituents, the number of substituents, and the positions of the substituents.

According to the present invention, it is possible to provide a resin composition capable of obtaining a cured coating film having excellent heat resistance and coating film appearance. Further, according to the present invention, it is possible to provide a cured product obtained using the resin composition and an article using the cured product.

1 is a GPC chart of maleimide resin (A-1) obtained in Synthesis Example 1. FIG. 2 is a GPC chart of maleimide resin (A-2) obtained in Synthesis Example 2. FIG. 3 is a GPC chart of maleimide resin (A-3) obtained in Synthesis Example 3. FIG. FIG. 2 is a GPC chart of maleimide resin (A-4) obtained in Synthesis Example 4. FIG. 2 is a GPC chart of maleimide resin (A-5) obtained in Synthesis Example 5. FIG. 2 is a GPC chart of maleimide resin (A-6) obtained in Synthesis Example 6.

(Explanation of terms)
Unless otherwise specified in this specification, the following terminology is applicable.

In this specification, examples of the "aryl group" include a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group, and the like. In addition, the "aryl group" means that the hydrogen atom of the aromatic ring in the aryl group is 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. Good too.

In this specification, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, a naphthylmethyl group, and the like.

In this specification, "alkyl group" includes, 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, 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 this specification, "alkoxy group (alkyloxy group)" includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyl group, etc. Examples include oxy group and nonyloxy group.

In this specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In this specification, "alkylene group" 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 etc.

In this specification, the "monovalent hydrocarbon group" includes, for example, the above alkyl group, and one or more -CH ₂ -s in the alkyl group are arranged so that -O- or It may be substituted with -S-, or one or more -CH ₂ -CH ₂ - in the alkyl group may be substituted with -CH=CH- so that they are not adjacent to each other.

In this specification, the "divalent hydrocarbon group" includes, for example, the above-mentioned alkylene group, and _-O- or It may be substituted with -S-, or one or more -CH ₂ -CH ₂ - in the alkylene group may be substituted with -CH=CH ₂ - so that they are not adjacent to each other.

In this specification, "maleimide resin" means a resin having a maleimide group. As used herein, "maleimide compound" means a compound having a maleimide group.

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)acrylic" means acrylic and/or methacryl.

Hereinafter, an embodiment of the present invention (sometimes referred to as "this embodiment") will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist. It can be implemented by

で示される第１の芳香環－マレイミド骨格と、下記一般式（２）：

で示される第２の芳香環－マレイミド骨格とを有するマレイミド化合物（ａ）を含む。ここで式（１）及び式（２）中、Ｒ^１～Ｒ^４は、それぞれ独立して、水素、メチル基又はエチル基を表し、Ａｒ^１及びＡｒ^２は、それぞれ独立して、１つ以上の置換基を有してもよい芳香環を表し、＊は、前記芳香環から他の部位への結合を表し、但し、Ａｒ^１及びＡｒ^２は、置換基の種類、置換基の数、及び置換基の位置の少なくともいずれかが互いに異なる。
かかる樹脂組成物によれば、優れた耐熱性及び塗膜外観性を有する硬化塗膜を得ることが可能である。 [Resin composition]
The resin composition of this embodiment is a resin composition containing a maleimide resin (A) and a compound (B) having a polymerizable unsaturated group (hereinafter also referred to as "component (B)"). The maleimide resin (A) contains the following general formula (1) in one molecule:

The first aromatic ring-maleimide skeleton represented by the following general formula (2):

It includes a maleimide compound (a) having a second aromatic ring and a maleimide skeleton represented by: Here, in formula (1) and formula (2), R ¹ to R ⁴ each independently represent hydrogen, a methyl group, or an ethyl group, and Ar ¹ and Ar ² each independently represent one or more represents an aromatic ring that may have a substituent, * represents a bond from the aromatic ring to another site, provided that Ar ¹ and Ar ² represent the type of substituent, the number of substituents, and At least one of the positions of the substituents is different from each other.
According to such a resin composition, it is possible to obtain a cured coating film having excellent heat resistance and coating film appearance.

The content of maleimide resin (A) in the total amount (100% by mass) of the resin composition of this embodiment is preferably 1% by mass or more, and 5% by mass from the viewpoint of improving heat resistance and coating film appearance in a well-balanced manner. The content is more preferably 10% by mass or more, even more preferably 20% by mass or more. Further, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

In addition, the content of component (B) in the total amount (100% by mass) of the resin composition of this embodiment is preferably 10% by mass or more, and 20% by mass from the viewpoint of improving heat resistance and coating film appearance in a well-balanced manner. % or more, more preferably 30% by mass or more, further preferably 99% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less.

In the resin composition of this embodiment, the content of the solid content of the maleimide resin (A) with respect to 100 parts by mass of the solid content of the compound (B) having a polymerizable unsaturated group is set to maintain a good balance between heat resistance and coating film appearance. From the viewpoint of improvement, the amount is preferably in the range of 1 to 10,000 parts by mass. From the same viewpoint, the content is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and also preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 200 parts by mass or less.

The resin composition of this embodiment may be substantially composed only of the maleimide resin (A) and the compound (B) having a polymerizable unsaturated group. Further, the resin composition of the present embodiment may further contain a photopolymerization initiator in addition to the maleimide resin (A) and the compound (B) having a polymerizable unsaturated group. Moreover, the resin composition of this embodiment may further contain an optionally added component as an optional component. Furthermore, the resin composition of the present embodiment may contain a maleimide resin (A), a compound having a polymerizable unsaturated group (B), a photopolymerization initiator, and optional additive components, as long as the effects of the present disclosure are not impaired. may contain unavoidable impurities.
The total content of the maleimide resin (A) and the compound having a polymerizable unsaturated group (B) in the total amount (100% by mass) of the resin composition of this embodiment improves heat resistance and coating film appearance in a well-balanced manner. From the viewpoint, the content is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 95% by mass or less, and more preferably 90% by mass or less.

Hereinafter, the maleimide resin (A), the compound having a polymerizable unsaturated group (B), the photopolymerization initiator, and optionally added components will be explained in order.

で示される第１の芳香環－マレイミド骨格と、下記一般式（２）：

で示される第２の芳香環－マレイミド骨格とを有するマレイミド化合物である。ここで式（１）及び式（２）中、Ｒ^１～Ｒ^４は、それぞれ独立して、水素、メチル基又はエチル基を表し、Ａｒ^１及びＡｒ^２（以下、これらを「Ａｒ」と総称することがある。）は、それぞれ独立して、１つ以上の置換基を有してもよい芳香環を表し、＊は、前記芳香環から他の部位への結合を表し、但し、Ａｒ^１及びＡｒ^２は、置換基の種類、置換基の数、及び置換基の位置（以下、これらを「置換基の形態」と総称することがある。）の少なくともいずれかが互いに異なる。マレイミド化合物（ａ）は、１種単独であってもよく、２種以上の組み合わせであってもよい。
このような、置換基の形態が互いに異なる２以上の芳香環－マレイミド骨格を有するマレイミド化合物（ａ）を用いることで、マレイミド単独での結晶性が低くなり、樹脂組成物における各成分の相溶性が高まる結果、耐熱性及び塗膜外観性を向上させることができる。 (Maleimide resin (A))
Maleimide resin (A) is one of the essential components in the resin composition of this embodiment. As mentioned above, the maleimide resin (A) is a resin containing at least the maleimide compound (a). The maleimide compound (a) has the following general formula (1) in one molecule:

The first aromatic ring-maleimide skeleton represented by the following general formula (2):

It is a maleimide compound having a second aromatic ring and a maleimide skeleton represented by Here, in formula (1) and formula (2), R ¹ to R ⁴ each independently represent hydrogen, a methyl group, or an ethyl group, and Ar ¹ and Ar ² (hereinafter collectively referred to as "Ar") ) each independently represents an aromatic ring which may have one or more substituents, * represents a bond from the aromatic ring to another site, provided that Ar ¹ and Ar ² differ from each other in at least one of the type of substituent, the number of substituents, and the position of the substituent (hereinafter, these may be collectively referred to as "the form of the substituent"). The maleimide compound (a) may be used alone or in combination of two or more.
By using such a maleimide compound (a) having two or more aromatic ring-maleimide skeletons with different forms of substituents, the crystallinity of maleimide alone becomes low, and the compatibility of each component in the resin composition is reduced. As a result, heat resistance and coating film appearance can be improved.

In addition to the maleimide compound (a), the maleimide resin (A) includes a maleimide compound other than the maleimide compound (a) (for example, a maleimide having two or more aromatic rings-maleimide skeletons with all the substituents having the same form). compounds, etc.).
Further, in formula (1) and formula (2), only one * (bond from the aromatic ring to another site) is shown for convenience, but the number of such bonds * is not limited to this. The number may be two or three.

R ¹ to R ⁴ in formula (1) and formula (2) are each independently hydrogen, methyl group, or ethyl group, but from the viewpoint of reactivity of maleimide, hydrogen or methyl group is preferable. Preferably, all hydrogen is more preferable. Further, from the viewpoint of ease of manufacture, it is preferable that the combination of R ¹ and R ² is the same as the combination of R ³ and R ⁴ .

Examples of the aromatic rings of Ar ¹ and Ar ² in formulas (1) and (2) include benzene, naphthalene, anthracene, and the like. The aromatic rings of Ar ¹ and Ar ² may be the same or different.

Examples of the substituents that the aromatic rings of Ar ¹ and Ar ² may have include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, alkynyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups. Can be mentioned.

The aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, and may have an unsaturated bond in its structure. Specifically, the aliphatic hydrocarbon groups mentioned above include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Examples include groups.
Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like.
Examples of the alkenyloxy group include an allyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a group in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, alkyloxy group, or halogen atom.
Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a group in which an alkyl group, the above-mentioned alkyloxy group, or a halogen atom is substituted on the aromatic nucleus of these groups.
In particular, the aromatic rings of Ar ¹ and Ar ² preferably each have an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group). , butyl group, etc.).

Further, the number of substituents that the aromatic rings of Ar ¹ and Ar ² may have includes 0, 1, 2, 3, and 4, and when the aromatic ring is other than benzene, The number may be 5 or more. When it has two or more substituents, they may be the same or different. In particular, it is preferable that both the aromatic rings of Ar ¹ and Ar ² have at least one substituent.

In addition, the position of the substituent that the aromatic rings of Ar ¹ and Ar ² may have is the carbon adjacent to the carbon to which the maleimide group is bonded in the aromatic ring (i.e., the ortho position in the case where the aromatic ring is benzene). ), the two carbon atoms next to the carbon to which the maleimide group is bonded (i.e., the meta position in the above case), and the three carbon atoms next to the carbon atom to which the maleimide group is bonded (i.e., the para position in the above case). It will be done. In particular, it is preferable that the aromatic rings of Ar ¹ and Ar ² each have at least a substituent at one or both carbon positions (ortho position) adjacent to the carbon to which the maleimide group is bonded.

When the aromatic rings of Ar ¹ and Ar ² are benzene, the bond * to another site preferably extends from the para position with respect to the maleimide group in the aromatic ring.

Ar ¹ and Ar ^{2 in formulas (1) and (2} ) are required to be different from each other in at least one of the types of substituents, the number of substituents, and the positions of the substituents. Examples of the above-mentioned "different from each other" are not particularly limited, and include the following.
[1] Different types of substituents (specific example: methyl group for one Ar, ethyl group for the other Ar)
[2] The number of substituents is different (specific example: one for one Ar, two for the other Ar)
[3] The positions of the substituents are different (specific example: when the aromatic rings of Ar ¹ and Ar ² are benzene, one Ar is at the ortho position and the other is at the meta position)
[4] Any combination of the above [1] to [3] (specific example: when the aromatic rings of Ar ¹ and Ar ² are benzene, one Ar has an ethyl group at one position ortho to the maleimide group) one methyl group at both positions ortho to the maleimide group on the other Ar)

The number of aromatic ring-maleimide skeletons in one molecule of maleimide compound (a) must be 2 or more, but may be 2 (i.e., dinuclear component (bismaleimide compound)), or 3 (ie, trinuclear component (trismaleimide compound)), four (ie, tetranuclear component), or five or more.
Here, in this specification, the "number of nuclear bodies" refers to the number of aromatic ring-maleimide skeletons in one molecule. The aromatic ring-maleimide skeleton is typically a skeleton derived from an aromatic monoamine compound that is a reaction raw material.

Specifically, the maleimide compound (a) includes a dinuclear component represented by the following formula (3-1), a trinuclear component represented by the following formula (3-2), and a trinuclear component represented by the following formula (3-3). A relatively low molecular weight component such as a tetranuclear component represented by the following formula (3-4) is preferable.

［式中、Ａは、芳香環－マレイミド骨格であり、Ｂは、任意に選択される部位である。式中のＡ及びＢは、それぞれ同一であってもよいし、異なっていてもよい。］

[In the formula, A is an aromatic ring-maleimide skeleton, and B is an arbitrarily selected moiety. A and B in the formula may be the same or different. ]

When the number of aromatic ring-maleimide skeletons in one molecule is 3 or more, and the forms of substituents on at least two of the aromatic rings are different from each other, the compound falls under maleimide compound (a).

In particular, the maleimide resin (A) preferably contains a binuclear component (bismaleimide compound). Further, the proportion of the binuclear component (bismaleimide compound) in the maleimide resin (A) is preferably 30% or more, more preferably 50% or more.
The content of the binuclear component in the maleimide resin (A) is a value calculated from the area ratio of a gel permeation chromatography (GPC) chart. The measurement conditions for gel permeation chromatography (GPC) are as shown in Examples below.

［ここで式（３－５）中、Ｒ^１～Ｒ^４、Ａｒ^１及びＡｒ^２は、式（１）及び式（２）における定義に同じであり、Ｚは、炭素原子数１～２００の有機基である。］で示される非対称ビスマレイミド化合物（２核体成分）であることが好ましい。本実施形態においては、当該非対称ビスマレイミド化合物を単離精製して用いてもよい。 The maleimide compound (a) is an asymmetric bismaleimide in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1 to 200 carbon atoms. Preferably, it is a compound. More specifically, the following general formula (3-5):

[Here, in formula (3-5), R ¹ to R ⁴ , Ar ¹ and Ar ² are the same as defined in formula (1) and formula (2), and Z is a carbon atom having 1 to 200 carbon atoms. It is an organic group. ] An asymmetric bismaleimide compound (binuclear component) is preferable. In this embodiment, the asymmetric bismaleimide compound may be isolated and purified before use.

When the aromatic rings of Ar ¹ and Ar ² in formula (3-5) are benzene, the position of the bond from the aromatic ring to Z is preferably the para position with respect to the maleimide group.

Z in the above formula (3-5) is typically a moiety derived from a binder that is a reaction raw material. Z is a divalent organic group having 1 to 200 carbon atoms, but as long as the number of carbon atoms is in the range of 1 to 200, it may be a moiety containing other atoms such as an oxygen atom or a halogen atom. . Among these, Z is preferably a divalent organic group having 1 to 20 carbon atoms. Specific examples of the above Z include, for example, moieties represented by the following general formulas (Z-1) to (Z-8).

R ⁵ in general formula (Z-1) each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an aromatic ring which may have a substituent.
The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, and the like.
Examples of the aromatic ring which may have a substituent include a phenyl group, a naphthyl group, and a structural moiety having one or more of various substituents on these aromatic rings. Examples of the above-mentioned substituents include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups.
The aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, and may have an unsaturated bond in its structure. Specifically, the aliphatic hydrocarbon groups mentioned above include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Examples include groups.
Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like.
Examples of the alkenyloxy group include an allyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a group in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, alkyloxy group, or halogen atom.
Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a group in which an alkyl group, the above-mentioned alkyloxy group, or a halogen atom is substituted on the aromatic nucleus of these groups.

Ar ³ in the general formulas (Z-2), (Z-3), and (Z-8) each independently represents an aromatic ring which may have a substituent. Specific examples of Ar ³ include phenylene groups, naphthylene groups, and those having one or more of various substituents on their aromatic rings. Examples of the above-mentioned substituents include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups.
The aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, and may have an unsaturated bond in its structure. Specifically, the aliphatic hydrocarbon groups mentioned above include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Examples include groups.
Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like.
Examples of the alkenyloxy group include an allyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a group in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, alkyloxy group, or halogen atom.
Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a group in which an alkyl group, the above-mentioned alkyloxy group, or a halogen atom is substituted on the aromatic nucleus of these groups.

R ⁶ in the above general formulas (Z-2) and (Z-3) each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, and the like.

Y in the above general formula (Z-3) represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group. The divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure.

R ⁸ in the above general formula (Z-4) is each independently an aliphatic hydrocarbon group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, or an aralkyl group, is an integer of 0 to 3, and n is an integer of 1 or more.
The aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure. Specific examples of aliphatic hydrocarbon groups include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Examples include groups.
Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like.
Examples of the alkenyloxy group include an allyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a group in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, alkyloxy group, or halogen atom.
Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a group in which an alkyl group, the above-mentioned alkyloxy group, or a halogen atom is substituted on the aromatic nucleus of these groups.

R ⁷ in the above general formula (Z-7) is a divalent aliphatic hydrocarbon group other than that represented by the general formula (Z-1), an aromatic group which may have a substituent, or represents the combination. The divalent aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure.

<Production of maleimide resin (A)>
Maleimide resin (A) (i.e., resin containing maleimide compound (a)) produces a polyamine compound by reacting multiple types of aromatic monoamine compounds (i.e., different forms of substituents) with a binder. Then, the polyamine compound is converted into maleimide. The structures of the plurality of types of aromatic monoamine compounds described above contribute to the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton in the resulting maleimide compound (a).

As the above-mentioned aromatic monoamine compound, a wide variety of compounds can be used without any particular limitations on other specific structures as long as they have one NH ₂ on the aromatic ring. Specific examples of the aromatic monoamine compound include compounds having one _NH2 group on the aromatic ring, and compounds having one or more substituents in addition to the _NH2 group on the aromatic ring. It will be done.

Examples of the aromatic ring include benzene, naphthalene, anthracene, and the like.

Examples of the above-mentioned substituents include aliphatic hydrocarbon groups, alkyloxy groups, alkenyloxy groups, alkynyloxy groups, halogen atoms, aryl groups, aralkyl groups, and hydroxyl groups. In addition, the said substituent corresponds substantially to the substituent which the aromatic ring of ^Ar1 and ^Ar2 in the maleimide compound (a) obtained is. Therefore, specific examples of the above substituents are as described above.

Among the aromatic monoamine compounds, it is preferable to use aniline, a compound having a substituent at the 2-position of aniline, and/or a compound having a substituent at the 2-, 6-position of aniline. In addition, in the case of a compound having a substituent at the 2-position of aniline and a compound having a substituent at the 2,6-position of aniline, the substituent is a maleimide resin that has excellent heat resistance in the cured product, so carbon An aliphatic hydrocarbon group having 1 to 4 atoms is preferable, and an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.) is more preferable.

In this embodiment, as described above, a plurality of types of the aromatic monoamine compounds are used. This results in a maleimide resin that has a low melting point and softening point and excellent handling properties while maintaining the high heat resistance characteristic of maleimide resins, and exhibits the desired effects. The number of types of aromatic monoamine compounds to be used may be 2 or more types, while the upper limit is not particularly limited, but it is preferably in the range of 2 to 5 types because it can be produced relatively easily. More preferably, there are two or three types.

In addition, the amount of each aromatic monoamine compound to be used should be at least 10% by mass or more based on the total amount of aromatic monoamine compounds, so that the effect of improving heat resistance and coating film appearance is sufficiently exhibited. The content is preferably 25% by mass or more, and more preferably 25% by mass or more. Further, the amount of each aromatic monoamine compound used is preferably 90% by mass or less, more preferably 75% by mass or less, based on the total amount of aromatic monoamine compounds. In particular, when two types of aromatic monoamine compounds are used, the mass ratio of the two is preferably in the range of 10/90 to 90/10, more preferably in the range of 20/80 to 80/20. .

As the binder, various compounds can be used without any particular limitations on its specific structure as long as it is a compound that reacts with the aromatic monoamine compound and bonds the aromatic rings of the aromatic monoamine compound to each other. The binder may be used alone or in combination of two or more. Specific examples of the binder include aldehyde compound (B-1) and ketone compound (B-2).
Examples of the aldehyde compound (B-1) include aliphatic aldehyde compounds such as formaldehyde and acetaldehyde, and aromatic aldehyde compounds such as benzaldehyde and naphthaldehyde. The aldehyde compound (B-1) may be used alone or in combination of two or more.
Examples of the ketone compound (B-2) include aliphatic ketone compounds such as acetone, methyl ethyl ketone and diethyl ketone, and aromatic ketone compounds such as acetophenone. The ketone compound (B-2) may be used alone or in combination of two or more.

Further, as specific examples of the binder, aromatic compounds (B-3) represented by the following general formula (B-3), aromatic compounds (B-3) represented by the following general formula (B-4), 4), an aromatic compound (B-5) represented by the following general formula (B-5), an aromatic compound (B-6) represented by the following general formula (B-6), an aromatic compound (B-6) represented by the following general formula (B-5), -7), an aromatic compound (B-7) represented by the following general formula (B-8), and the like.

Ar ³ in the above general formulas (B-3) to (B-6) each independently represents an aromatic ring which may have a substituent. Specific examples of Ar ³ include those similar to Ar ³ in the above-mentioned general formulas (Z-2), (Z-3), and (Z-8).

R ⁹ in the above general formulas (B-3) and (B-5) is each independently a hydrogen atom or a methyl group.

R ¹⁰ in the above general formulas (B-4) and (B-6) each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, vinyl group, propyl group, allyl group, butyl group, and the like.

R ⁸ in the above general formulas (B-7) and (B-8) is each independently an aliphatic hydrocarbon group, an alkyloxy group, an alkenyloxy group, an alkynyloxy group, a halogen atom, an aryl group, or It represents an aralkyl group, and l is an integer of 0 to 3. Specific examples of R ⁸ include those similar to R ⁸ in the above-mentioned general formula (Z-4).

X in the above general formulas (B-4), (B-6), and (B-8) represents a hydroxyl group, a halogen atom, or an alkyloxy group. Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and the like.

Y in the above general formulas (B-5) and (B-6) represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group. The divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms may have a linear, branched, or cyclic structure, and may have an unsaturated bond in the structure.

Examples of the step of producing a polyamine compound by reacting a plurality of aromatic monoamine compounds with a binder include a method in which a plurality of aromatic monoamine compounds and a binder are reacted under acidic catalytic conditions. It will be done. In particular, it is preferable to add the binder in portions to the aromatic monoamine compound because reaction control becomes easier. The reaction may be carried out in an appropriate solvent. Furthermore, in the above step, the reaction can proceed efficiently by heating to about 50 to 200°C. After the reaction is completed, the intermediate polyamine compound can be obtained by washing with an alkaline aqueous solution, distilled water, or the like.

Examples of the acidic catalyst include para-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, sulfuric acid, hydrochloric acid, oxalic acid, activated clay, and the like. One type of acidic catalyst may be used alone, or two or more types may be used in combination. The amount of the acidic catalyst added is preferably in the range of 0.01 to 0.5 mol, and preferably in the range of 0.1 to 0.3 mol, per 2 mol of the aromatic monoamine compound. More preferred. If the number of moles cannot be defined, the ratio is preferably in the range of 1% by mass to 50% by mass based on the total amount of the aromatic monoamine compound, binder, solvent and acidic catalyst.

Examples of the solvent include distilled water and organic solvents such as toluene and xylene. One type of solvent may be used alone, or two or more types may be used in combination. The amount of the solvent used is preferably in the range of 5% by mass to 100% by mass based on the total amount of the aromatic monoamine compound and the binder.

Next, the step of maleimidizing the intermediate polyamine compound (maleimidization reaction) includes, for example, a method of reacting the polyamine compound and an acid anhydride under acidic catalytic conditions. In particular, it is preferable to add the acid anhydride in portions to the polyamine compound, or to dissolve the acid anhydride in an appropriate solvent and dropwise add the acid anhydride, since this facilitates reaction control. The reaction may be carried out in an appropriate solvent. The reaction procedure is to first stir a polyamine compound and an acid anhydride at room temperature to obtain an amic acid intermediate, then add an acid catalyst and heat to 50 to 200°C, more preferably 70 to 150°C. It is preferable to allow the reaction to proceed. At this time, it is preferable to remove moisture within the system. After the reaction is completed, the desired maleimide resin (A) can be obtained by washing with an alkaline aqueous solution, distilled water, or the like.

Examples of the acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and the like. One type of acid anhydride may be used alone, or two or more types may be used in combination.

Examples of the acidic catalyst include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. One type of acidic catalyst may be used alone, or two or more types may be used in combination. The amount of the acidic catalyst added is usually 0.01 to 10 mol, preferably 0.03 to 3 mol, per 1 g/mol of the amino group equivalent of the polyamine compound.

The above-mentioned solvent is not particularly limited as long as it can dissolve the polyamine compound and acid anhydride. In particular, since the solubility of polyamine compounds and acid anhydrides is high and the reaction proceeds efficiently, a mixed solvent of a non-polar solvent such as toluene and an aprotic polar solvent such as dimethylformamide is used as the solvent. It is preferable to use Examples of the non-polar solvent include toluene, xylene, chlorobenzene, and the like. In addition, examples of the aprotic polar solvent include dimethyl formaldehyde, methyl ethyl ketone, and the like. The blending ratio of both and the amount of solvent used can be adjusted as appropriate depending on the solubility of the polyamine compound and acid anhydride. As an example, the mass ratio of the nonpolar solvent to the aprotic solvent is in the range of 1/99 to 99/1, and the total amount of the solvent is 0.00% relative to the total amount of the polyamine compound, acid anhydride, and all solvents. It can be in the range of 5 to 80% by mass.

(Compound (B) having a polymerizable unsaturated group)
The compound (B) having a polymerizable unsaturated group is one of the essential components in the resin composition of this embodiment. The component (B) only needs to have a polymerizable unsaturated group, and other specific structures or molecular weights are not particularly limited, and a wide variety of resins or compounds can be used. The compound (B) having a polymerizable unsaturated group may be used alone or in combination of two or more. Note that the compound (B) having a polymerizable unsaturated group preferably has a polymerizable unsaturated group but does not have an acid group.

In this embodiment, the polymerizable unsaturated group contained in component (B) includes, for example, a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group. Examples include groups.

Specific examples of the compound (B) having a polymerizable unsaturated group include a (meth)acrylate compound (B0), a resin having a polymerizable unsaturated group, and the like.

The (meth)acrylate compound (B0) is not particularly limited as long as it has a (meth)acryloyl group, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl ( Aliphatic mono(meth)acrylate compounds such as meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate; cyclohexyl(meth)acrylate, isobornyl(meth)acrylate Alicyclic mono(meth)acrylate compounds such as acrylate and adamantyl mono(meth)acrylate; Heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; Benzyl(meth)acrylate, phenyl( meth)acrylate, phenylbenzyl(meth)acrylate, phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as acrylate, benzylbenzyl(meth)acrylate, and phenylphenoxyethyl(meth)acrylate: In the molecular structure of the various mono(meth)acrylate monomers, (Poly)oxyalkylene-modified mono(meth)acrylate compounds into which polyoxyalkylene chains such as poly()oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. are introduced; the various mono(meth)acrylates mentioned above Lactone-modified mono(meth)acrylate compounds with a (poly)lactone structure introduced into the molecular structure of the compound; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate Aliphatic di(meth)acrylate compounds such as (meth)acrylate, neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate; ) acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and other alicyclic di(meth)acrylate compounds; biphenol di(meth)acrylate, bisphenol di(meth)acrylate, etc. Aromatic di(meth)acrylate compounds; The various di(meth)acrylate compounds mentioned above have (poly)oxy groups such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in their molecular structures. Polyoxyalkylene-modified di(meth)acrylate compounds with an alkylene chain introduced; lactone-modified di(meth)acrylate compounds with a (poly)lactone structure introduced into the molecular structure of the various di(meth)acrylate compounds mentioned above; trimethylolpropane Aliphatic tri(meth)acrylate compounds such as tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyethylene chains and (poly)oxypropylene chains in the molecular structure of the aliphatic tri(meth)acrylate compounds. , a (poly)oxyalkylene-modified tri(meth)acrylate compound into which a (poly)oxyalkylene chain such as a (poly)oxytetramethylene chain is introduced; (poly)lactone in the molecular structure of the aliphatic tri(meth)acrylate compound Lactone-modified tri(meth)acrylate compounds with introduced structures; aliphatic poly(meth)acrylates with four or more functionalities such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Acrylate compound; (poly)oxyalkylene chain such as (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound 4 (poly)oxyalkylene-modified poly(meth)acrylate compound having more than four functional functions; lactone-modified poly(meth)acrylate compound having four or more functionalities in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; ;Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri (meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditri (Meth)acrylate compounds having a hydroxyl group such as methylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; A (poly)oxyalkylene modified product into which a (poly)oxyalkylene chain such as a poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced; a molecule of the (meth)acrylate compound having the above hydroxyl group Lactone modified product with a (poly)lactone structure introduced into the structure; (meth) having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate Acrylate compounds: (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, droxybenzene diglycidyl ether, dihydroxynaphthalene Examples include (meth)acrylate compounds having an epoxy group, such as mono(meth)acrylates of diglycidyl ether compounds such as diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether.
The (meth)acrylate compound (B0) may be used alone or in combination of two or more.

The resin having a polymerizable unsaturated group may be any resin as long as it has a polymerizable unsaturated group in the resin, for example, the following [1] to [6]:
[1] Epoxy resin (B1) having a polymerizable unsaturated group,
[2] Urethane resin (B2) having a polymerizable unsaturated group,
[3] Acrylic resin (B3) having a polymerizable unsaturated group,
[4] Amidimide resin (B4) having a polymerizable unsaturated group,
[5] Acrylamide resin (B5) having a polymerizable unsaturated group,
[6] Ester resin (B6) having a polymerizable unsaturated group,
etc.

<Epoxy resin (B1) having a polymerizable unsaturated group>
As the epoxy resin (B1) having a polymerizable unsaturated group, for example, an epoxy (meth)acrylate resin obtained by reacting an epoxy resin, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride; Epoxy (meth)acrylate resin having a urethane group obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polybasic acid anhydride. ; etc. Note that, as described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B1), but it is preferable not to use it. The resin (B1) preferably has a polymerizable unsaturated group but no acid group.

Examples of the above epoxy resin 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 novolak type epoxy resin, naphthol-phenol cocondensed novolak type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin , phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type Examples include epoxy resins and oxazolidone-type epoxy resins. These epoxy resins may 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, and bisphenol S type epoxy resin. Examples include resin.
Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, and hydrogenated bisphenol S epoxy resin. Examples include resin.

Examples of the above biphenol epoxy resin include 4,4'-biphenol epoxy resin, 2,2'-biphenol epoxy resin, tetramethyl-4,4'-biphenol epoxy resin, and tetramethyl-2,2' -Biphenol type epoxy resins, etc.
Examples of the hydrogenated biphenol epoxy resin include hydrogenated 4,4'-biphenol epoxy resin, hydrogenated 2,2'-biphenol epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol epoxy resin. , hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.

［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。］で表される化合物等も用いることができる。 Examples of the unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and the like. Furthermore, esters, acid halides, acid anhydrides, and the like of the above-mentioned unsaturated monobasic acids can also be used. Furthermore, as the unsaturated monobasic acid, the following general formula (4):

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

［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^５１は１～５の整数を表す。］で表される（ポリ）エステル鎖が挙げられる。
これら不飽和一塩基酸は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.
As the above (poly)ester chain, for example, the following general formula (5):

[In the above general formula (5), R ⁵¹ and R ⁵² represent an alkylene group having 1 to 10 carbon atoms, and n ⁵¹ represents an integer of 1 to 5. ] Examples include (poly)ester chains represented by the following.
These unsaturated monobasic acids may be used alone or in combination of two or more.

Examples of the aromatic hydrocarbon chain include phenylene chain, naphthylene chain, biphenylene chain, phenylnaphthylene chain, and binaphthylene chain. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring can also be used.

［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。］で表される（ポリ）カーボネート鎖が挙げられる。 As the above (poly)carbonate chain, for example, the following general formula (6):

[In the above 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. ] Examples include (poly)carbonate chains represented by the following.

Examples of the polybasic acid anhydrides include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, 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. Examples include acid anhydrides of acids, glutaconic acid, and 1,2,3,4-butanetetracarboxylic acid. Moreover, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either a linear type or a branched type, and may have an unsaturated bond in the structure.

In the present invention, as the above-mentioned alicyclic polybasic acid anhydride, those in which an acid anhydride group is bonded to an alicyclic structure are defined as alicyclic polybasic acid anhydrides, and aromatic rings in other structural parts are defined as alicyclic polybasic acid anhydrides. It does not matter whether or not it exists. 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 anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, Examples include acid anhydride of benzophenone tetracarboxylic acid.
These polybasic acid anhydrides may be used alone or in combination of two or more.

［上記一般式（７）中、Ｒ^７２及びＲ^７３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^７１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、ｋ^７１は０又は１～３の整数であり、ｎ^７１は１以上の整数である。］ Examples of the polyisocyanate compounds 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, Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate and other aromatic diisocyanate compounds; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (7); isocyanurate modified products, biuret modified products thereof, Examples include modified allophanate. These polyisocyanate compounds may be used alone or in combination of two or more.

[In the above general formula (7), R ⁷² and R ⁷³ each independently represent either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ⁷¹ each independently, It represents an alkyl group having 1 to 4 carbon atoms, k ⁷¹ is 0 or an integer of 1 to 3, and n ⁷¹ is an integer of 1 or more. ]

Examples of (meth)acrylate compounds having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol (meth)acrylate. , pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate 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, (poly)oxytetramethylene chains, etc. are introduced into the molecular structures of the (meth)acrylate compounds having various hydroxyl groups. (Poly)oxyalkylene modified products and lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the (meth)acrylate compounds having various hydroxyl groups can also be used.

The method for producing the epoxy resin (B1) having a polymerizable unsaturated group is not particularly limited, and any method may be used. In the production of the epoxy resin (B1) having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

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, dimethyl formamide, methyl isobutyl ketone, cyclohexanone, and dimethyl acetamide; and tetrahydrofuran and dioxolane. 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; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol; 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, etc. It will be done. These organic solvents may be used alone or in combination of two or more.

Furthermore, as the above-mentioned organic solvent, commercially available products can be used, and examples of the commercially available products include "No. 1 Spindle Oil", "No. 3 Solvent", "No. 4 Solvent", and "No. 5 Solvent" manufactured by ENEOS Corporation. "Solvent", "Solvent No. 6", "Naftesol 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", "Diyaren 168"; "F Oxocol", "F Oxocol 180" manufactured by Nissan Chemical Co., Ltd.; "Supersol LA35", "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; "Exsol D80" manufactured by ExxonMobil Chemical Co., Ltd. ”, “Exor D110”, “Exor D120”, “Exor D130”, “Exor D160”, “Exor D100K”, “Exor D120K”, “Exor D130K”, “Exor D280”, “Exor D300”, “Exor D320” ”; etc.

Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 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 - Amine compounds such as aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; Quaternary compounds such as trioctylmethylammonium chloride and trioctylmethylammonium acetate Ammonium salts; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride , triphenylphosphonium chloride, benzylphosphonium chloride and other phosphonium salts; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1 , 1,3,3-tetrabutyl-1,3-dodecanoyl distanoxane; organometallic compounds such as zinc octylate, bismuth octylate; inorganic tin compounds such as tin octoate; inorganic metal compounds, etc. can be mentioned. Furthermore, 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.

<Urethane resin (B2) having polymerizable unsaturated group>
The urethane resin (B2) having a polymerizable unsaturated group is, for example, a resin obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and if necessary a polyol compound and/or a polybasic acid anhydride. Examples include those that were given. Note that, as described above, polybasic acid anhydride can be used as a reaction raw material for resin (B2), but it is preferable not to use it. The resin (B2) preferably has a polymerizable unsaturated group but no acid group.

The polyisocyanate compound, the (meth)acrylate compound having a hydroxyl group, and the polybasic acid anhydride are the same as those already described for the resin (B1) and the like.

Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol. Polyol compound; (poly)oxyalkylene in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of the various polyol compounds mentioned above. Modified products; lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the various polyol compounds mentioned above, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid etc. The above polyol compounds may be used alone or in combination of two or more.

The method for producing the urethane resin (B2) having a polymerizable unsaturated group is not particularly limited, and any method may be used. In the production of the urethane resin (B2) having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary. In that case, the organic solvent and basic catalyst are the same as those already described for the resin (B1) and the like.

<Acrylic resin (B3) having a polymerizable unsaturated group>
As the acrylic resin (B3) having a polymerizable unsaturated group, for example, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group is polymerized as an essential component. A reaction product obtained by introducing a (meth)acryloyl group by further reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups. and, if necessary, those obtained by reacting the hydroxyl group in the reaction product with a polybasic acid anhydride. Note that, as described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B3), but it is preferable not to use it. The resin (B3) preferably has a polymerizable unsaturated group but no acid group.

In addition to the (meth)acrylate compound (α), the acrylic resin intermediate may be one obtained by copolymerizing other compounds having polymerizable unsaturated groups as necessary. Examples of the other compounds having polymerizable unsaturated groups include (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ) Acrylic acid alkyl ester; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, Examples include aromatic ring-containing (meth)acrylates such as phenoxyethyl acrylate; (meth)acrylates having a silyl group such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene.
The other compounds having polymerizable unsaturated groups may be used alone or in combination of two or more.

The above (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the above (meth)acrylate compound (α), but from the viewpoint of reactivity it should be the following combination: is preferred. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more.

The polybasic acid anhydride is the same as that already described for the resin (B1) and the like.

The method for producing the acrylic resin (B3) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (B3) having a polymerizable unsaturated group may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary. In that case, the organic solvent and basic catalyst are the same as those already described for the resin (B1) and the like.

<Amidimide resin (B4) having a polymerizable unsaturated group>
Examples of the amide-imide resin (B4) having a polymerizable unsaturated group include an amide-imide resin having an acid group and/or an acid anhydride group, and a (meth)acrylate compound having a hydroxyl group and/or a (meth)acrylate compound having an epoxy group. A product obtained by reacting an acrylate compound with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group, if necessary. Can be mentioned. Note that the compound having a reactive functional group may or may not have a (meth)acryloyl group. In addition, it is preferable that the said resin (B4) has a polymerizable unsaturated group but does not have an acid group.

The above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group may have only either an acid group or an acid anhydride group, or may have both. However, from the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, acid anhydride is used as the above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group. It is preferable that it has a group, and it is more preferable that it has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH/g as measured under neutral conditions, ie, under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferable that the value measured under conditions where the acid anhydride group is ring-opened, such as in the presence of water, is in the range of 61 to 360 mgKOH/g.

Examples of the above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group include those obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials. In that case, the polyisocyanate compound and polybasic acid anhydride are the same as those already described for the resin (B1) and the like. Note that, as described above, polybasic acid anhydride can be used as a reaction raw material for resin (B4), but it is preferable not to use it.

Moreover, as a reaction raw material for the above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group, a polybasic acid can be used in combination in addition to the above-mentioned polyisocyanate compound and polybasic acid anhydride, 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 Examples include naphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. It will be done. Further, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids may be used alone or in combination of two or more.

The (meth)acrylate compound having a hydroxyl group is the same as that already described for the resin (B1) and the like.

Examples of (meth)acrylate compounds having an epoxy group include (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate. ; Examples include mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

The method for producing the above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group is not particularly limited, and any method may be used. In the production of the above-mentioned amide-imide resin (B4) having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary. In that case, the organic solvent and basic catalyst are the same as those already described for the resin (B1) and the like.

<Acrylamide resin (B5) having polymerizable unsaturated group>
The acrylamide resin (B5) having a polymerizable unsaturated group includes, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid. Examples include those obtained by reacting anhydrides and unsaturated monobasic acids. Note that, as described above, polybasic acid anhydride can be used as a reaction raw material for resin (B5), but it is preferable not to use it. The resin (B5) preferably has a polymerizable unsaturated group but no acid group.

［上記一般式（８．１）～（８．５）中、Ｒ^８１～Ｒ^８４、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^８５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^８５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もよく、一般式（８．５）では、１分子中に存在するベンゼン環のいずれ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^８５及びｋ^８１～ｋ^８５であることを示している。 The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (8.1) to (8.5).

[In the above general formulas (8.1) to (8.5), 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, , represents either an aryl group or a halogen atom, R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom or a methyl group, and j ⁸¹ to j ⁸⁵ each independently represent an integer of 0 or 1 or more. , preferably 0 or an integer from 1 to 3, more preferably 0 or 1. k ⁸¹ to k ⁸⁵ each independently represent an integer of 1 or more, preferably 2 or 3. ]
In addition, the position of the substituent on the aromatic ring in the above general formulas (8.1) to (8.5) is arbitrary. For example, in the naphthalene ring of the general formula (8.2), the position of the substituent on any ring In general formula (8.3), any hydrogen atom in the benzene ring present in one biphenyl molecule may be substituted, and in general formula (8.4), aralkyl It may be substituted with any hydrogen atom of the benzene ring present in one molecule, and in general formula (8.5), it may be substituted with any hydrogen atom of the benzene ring present in one molecule. This shows that the number of substituents in one molecule is j ⁸¹ to j ⁸⁵ and k ⁸¹ to k ⁸⁵ .

［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。］ Further, as the compound having a phenolic hydroxyl group, for example, a compound having at least one phenolic hydroxyl group in the molecule, a compound represented by any of the following general formulas (9.1) to (9.5), and Examples include reaction products that use formaldehyde and/or formaldehyde as an essential reaction raw material. Further, a novolac type phenol resin, etc., which uses one or more kinds of compounds having at least one phenolic hydroxyl group in the molecule as a reaction raw material can also be used.

[In the above general formulas (9.1) to (9.5), h ⁹¹ represents 0 or 1, and R ⁹¹ to R ⁹⁶ each independently represent a monovalent aliphatic hydrocarbon group, an alkoxy group, represents either a halogen atom, an aryl group, an aryloxy group or an aralkyl group, k ⁹¹ to k ⁹⁶ each independently represent 0 or an integer of 1 to 4, Z ⁹¹ to Z ⁹⁶ each independently, represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y ⁹¹ represents 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. ]

Specific examples of the above compounds include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, and 3-methyl Catechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3- Naphthalene diol, 1,5-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, polyphenylene ether diol, polynaphthylene ether diol, phenol novolac resin, cresol novolac resin, bisphenol novolac resin, naphthol Examples include novolac type resins, phenol aralkyl type resins, naphthol aralkyl type resins, and phenol resins having a cyclo ring structure.
The above-mentioned compounds having a phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, and the like. The alkylene oxides may be used alone or in combination of two or more. Among these, ethylene oxide or propylene oxide is preferable as the alkylene oxide.

Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. The alkylene carbonates may be used alone or in combination of two or more. Among these, ethylene carbonate or propylene carbonate is preferable as the alkylene carbonate.

Examples of the above N-alkoxyalkyl (meth)acrylamide compounds include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and N-methoxyethyl (meth)acrylamide. , N-ethoxyethyl (meth)acrylamide, N-butoxyethyl (meth)acrylamide, and the like. The above N-alkoxyalkyl (meth)acrylamide compounds may be used alone or in combination of two or more.

The polybasic acid anhydride and unsaturated monobasic acid are the same as those already described for the resin (B1) and the like.

The method for producing the acrylamide resin (B5) having a polymerizable unsaturated group is not particularly limited, and any method may be used. In the production of the acrylamide resin (B5) having a polymerizable unsaturated group, it may be carried out in an organic solvent as necessary, and a basic catalyst and an acidic catalyst may be used as necessary. In that case, the organic solvent and basic catalyst are the same as those already described for the resin (B1) and the like.

Examples of the acidic catalysts 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. Examples include. Furthermore, a solid acid catalyst having a strong acid such as a sulfonyl group can also be used. These acidic catalysts may be used alone or in combination of two or more.

<Ester resin (B6) having a polymerizable unsaturated group>
As the ester resin (B6) having a polymerizable unsaturated group, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or an alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride are reacted. Examples include those obtained by Note that, as described above, polybasic acid anhydride can be used as a reaction raw material for resin (B6), but it is preferable not to use it. The resin (B6) preferably has a polymerizable unsaturated group but no acid group.

The compound having a phenolic hydroxyl group, alkylene oxide, alkylene carbonate, unsaturated monobasic acid, and polybasic acid anhydride are the same as those already described for resin (B1), resin (B5), and the like.

The method for producing the ester resin (B6) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (B6) having a polymerizable unsaturated group may be carried out in an organic solvent if necessary, and a basic catalyst and an acidic catalyst may be used if necessary. In that case, the organic solvent, basic catalyst, and acidic catalyst are the same as those already described for resin (B1), resin (B5), and the like.

(Photopolymerization initiator)
As described above, the resin composition of the present embodiment may further contain a photopolymerization initiator in addition to the maleimide resin (A) and the compound (B) having a polymerizable unsaturated group. Note that the resin composition containing a photopolymerization initiator is, in other words, a curable resin composition. The photopolymerization initiators may be used alone or in combination of two or more.

An appropriate 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, or a nitrile compound. Further, 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 photopolymerization initiators; 2,4,6-trimethylbenzoyl-diphenyl - Acyl phosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds, and the like.

Further, 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.

Commercially available photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "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.), "Bicure-10", "Bicure-55" (manufactured by Stouffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo Corporation), "Sandray 1000" (manufactured by Sandoz Corporation) ), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), "Runtecure-1104" (manufactured by Runtec) etc.

When using a photopolymerization initiator, the content of the photopolymerization initiator in the resin composition of this embodiment is based on a total of 100 parts by mass of the maleimide resin (A) and the compound having a polymerizable unsaturated group (B). , preferably 0.1 parts by mass or more and 10 parts by mass or less.

(Optional addition ingredient)
As described above, the resin composition of this embodiment may further contain optional additive components within a range that does not deviate from the purpose. Examples of optional additive components include curing agents, curing accelerators, other resins, organic solvents, polymerization inhibitors, antioxidants, flame retardants, fillers, pigments, antifoaming agents, viscosity modifiers, leveling agents, and ultraviolet rays. Various additives such as stabilizers and storage stabilizers can be mentioned.

<Curing agent>
Examples of the curing agent include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), and among these, epoxy resins are preferred.

The epoxy resin is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinked network with the epoxy groups. Examples of epoxy resins include, but are not limited to, phenol novolak epoxy resins, cresol novolac epoxy resins, α-naphthol novolac epoxy resins, β-naphthol novolac epoxy resins, bisphenol A novolak epoxy resins, biphenyl novolac epoxy resins. Novolac type epoxy resins such as;
Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, phenol biphenylaralkyl type epoxy resins;
Bisphenol A epoxy resin, bisphenol AP epoxy resin, bisphenol AF epoxy resin, bisphenol B epoxy resin, bisphenol BP epoxy resin, bisphenol C epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S bisphenol type epoxy resin such as type epoxy resin, tetrabromobisphenol A type epoxy resin;
Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, 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, glycidylamine type epoxy resins of diaminodiphenylsulfone;
Diglycidyl ester type epoxy resins such as 2,6-naphthalene dicarboxylic 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 a phenol compound are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are preferred because of their dielectric properties. It is more preferable from the viewpoint of The above-mentioned epoxy resins may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin is preferably 120 to 400 g/eq, more preferably 150 to 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 better. On the other hand, when the epoxy equivalent of the epoxy resin is 400 g/eq or less, the heat resistance of the resulting cured product improves. This is preferable because it has an excellent balance between properties and dielectric loss tangent.

The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of improving heat resistance and coating appearance in a well-balanced manner.

Examples of the amine curing agent include, but are not limited to, diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), and N-aminoethylpiperazine. , menthene diamine (MDA), isophorone diamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine, and other aliphatic amines; -Xylene diamine (XDA), methanephenylene diamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylamino) Examples include aromatic amines such as methyl) phenol.

Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimelitate, glycerol tristrimelitate, maleic anhydride, tetrahydrophthalic anhydride, and methyl Tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methyl Examples include cyclohexenedicarboxylic anhydride.

Examples of the phenolic 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, triphenol methane type resin, Examples include tetraphenolethane type resins, aminotriazine-modified phenol resins, and the like.
Any of the other curing agents mentioned above may be used alone or in combination of two or more.

When using a curing agent, the content of the curing agent in the resin composition of this embodiment is 10 to 40 parts by mass based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B). is preferred. When the amount is 10 parts by mass or more, heat resistance and curability can be further improved, and when it is 40 parts by mass or less, a lower dielectric loss tangent and higher flexibility can be obtained.

<Curing accelerator>
Examples of the curing accelerator include, but are not limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, and the like. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite 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-based curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5, Examples thereof include 4,0]-undecene-7 (DBU) and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 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-based 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-based 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 above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

When using a curing accelerator, the content of the curing accelerator in the resin composition of the present embodiment is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the maleimide resin (A) and component (B). Preferably. When the content of the curing accelerator is 0.01 part by mass or more, curability can be more reliably improved. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, insulation reliability can be maintained sufficiently well. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B), and 5 parts by mass or more. More preferably, it is less than parts by mass.

<Other resins>
Other resins include, but are not particularly limited to, maleimide resins other than maleimide resin (A), polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, cyanate ester resins, styrene-anhydride resins, etc. Examples include maleic acid resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphoric acid esters, and phosphoric acid ester-carbonate copolymers. These other resins may be used alone or in combination of two or more.

When using other resins, the content of the other resins in the resin composition of this embodiment is preferably 50% by mass or less of the total amount.

<Organic solvent>
The organic solvent can have the function of adjusting the viscosity of the resin composition. Specific examples of organic solvents 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, 1,2,4-trimethylbenzene, etc. Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

When using an organic solvent, the content of the organic solvent in the resin composition of this embodiment is preferably 90% by mass or less, and 10 to 90% by mass based on the total amount (100% by mass) of the resin composition. The content is more preferably 20 to 80% by mass. It is preferable that the content of the organic solvent is 10% by mass or more because it provides excellent handling properties. On the other hand, it is preferable from the viewpoint of economic efficiency that the content of the organic solvent is 90% by mass or less.

<Polymerization inhibitor>
Examples of polymerization inhibitors include, but are not limited to, p-methoxyphenol (methoquinone), p-methoxycresol, 4-methoxy-1-naphthol, and 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- Phenol compounds such as 1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone , 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, N. N'-diphenyl-p-phenylenediamine, N-i-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, styrenated diphenylamine and 2,4,4-trimethyl Amine compounds such as the reaction product of pentene, the reaction product of diphenylamine and 2,4,4-trimethylpentene; phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy) }Thioether compounds such as methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate], ditridecane-1-yl 3,3'-sulfanediyl dipropanoate; N-nitrosodiphenylamine, N- Nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrone dimethylamine, p-nitrone -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-phenylhydroxylamine 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, 1-nitroso-2-naphthol-3,6-sulfone Nitroso compounds such as sodium acid, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride; phosphoric acid and octadecane- 1-ol ester, triphenylphosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, trisnonylphenylphosphite, Phosphite-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2 , 4-di-tert-butylphenyl) phosphite; zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, etc. ; Nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel; 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)- Sulfur compounds such as o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be mentioned. The polymerization inhibitors may be used alone or in combination of two or more.

<Antioxidant>
The antioxidant is not particularly limited, but the same compounds as those exemplified as polymerization inhibitors can be used. The antioxidants may be used alone or in combination of two or more.

Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S" and "Sumilizer GA" manufactured by Sumitomo Chemical Co., Ltd. -80ga'', etc.

<Flame retardant>
Examples of the flame retardant include, but are not particularly limited to, inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like. The flame retardants may be used alone or in combination of two or more.

Examples of the inorganic phosphorus flame retardant include, but are not limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

The organic phosphorus flame retardants mentioned above are not particularly limited, but include 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 such as diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphos 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 -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; the above-mentioned phosphoric acid ester, the above-mentioned diphenylphosphine, the above-mentioned phosphorus-containing phenol, and an epoxy resin or Examples include compounds obtained by reacting with aldehyde compounds and phenol compounds.

The above-mentioned halogen flame retardants include, but are not limited to, brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2,-bis(tetrabromophthalimide), 2, Examples include 4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and tetrabromophthalic acid.

When using a flame retardant, the amount of the flame retardant used in the resin composition of this embodiment is 0.1 to 50 parts by mass based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B). It is preferable that there be. When the content of the flame retardant is 0.1 parts by mass or more, flame retardancy can be imparted more reliably. On the other hand, when the content of the flame retardant is 50 parts by mass or less, 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, and 30 parts by mass or less, based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B). It is more preferable that

<Filler>
Examples of fillers include organic fillers and inorganic fillers. The organic filler has a function of improving elongation, a function of improving mechanical strength, etc. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and imparting flame retardancy. The above-mentioned fillers may be used alone or in combination of two or more.

Examples of the organic filler include, but are not particularly limited to, polyamide particles.

The above inorganic fillers include, but are not limited to, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and 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 the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used.

Further, the filler may be surface-treated if necessary. At this time, surface treatment agents that can be used include, but are not particularly limited to, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. 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, and hexamethyldimethoxysilane. Examples include silazane. In addition, the above-mentioned fillers may be used alone or in combination of two or more types.

When a filler is used, the amount of filler used in the resin composition of this embodiment is 0.5 to 95 parts by mass based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B). It is preferable that there be. When the content of the filler is 0.5 parts by mass or more, the effect of the filler can be sufficiently imparted. On the other hand, when the content of the filler is 95 parts by mass or less, deterioration of moldability due to the increase in the viscosity of the compound can be suppressed. From the same viewpoint, the content of the filler is more preferably 5 parts by mass or more, and 80 parts by mass or less, based on 100 parts by mass of the total amount of the maleimide resin (A) and component (B). It is more preferable that

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

[Cured product]
The cured product of this embodiment is a cured product of the resin composition (curable resin composition) described above. In other words, the cured product of this embodiment is obtained by curing the above-described resin composition (curable resin composition) by irradiating it with active energy rays. The cured product of this embodiment can function as an insulating material with excellent heat resistance and coating film appearance.

Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Furthermore, when ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, the irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere.

Examples of sources of ultraviolet light include ultraviolet lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps, sunlight, and LEDs. Ultraviolet lamps are commonly used from the viewpoint of performance and economy.

The cumulative amount of active energy rays is not particularly limited, but is preferably from 0.1 to 50 kJ/m ² , more preferably from 0.5 to 10 kJ/m ² . When the cumulative amount of light is within the above range, the occurrence of uncured portions can be sufficiently prevented or suppressed. Note that the irradiation with active energy rays may be performed in one step, or may be performed in two or more steps.

Further, as another method for obtaining a cured product by subjecting a curable resin composition to a curing reaction, for example, heat curing can be mentioned. The heating temperature during heat curing is not particularly limited, but it is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

The curable resin composition or cured product of this embodiment is used for circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, and adhesive films for build-up. Insulating 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. Can be mentioned. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and build-up adhesive films are used for so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. It can be used as an insulating material. Furthermore, among the above, the curable resin composition or cured product of this embodiment can be used as a semiconductor encapsulation material, semiconductor device, prepreg, flexible material, etc. by taking advantage of the characteristics that the cured product has excellent heat resistance and coating film appearance. It can be suitably applied to rubble wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials.

[Goods]
The article of this embodiment is characterized by having a coating film made of the above-mentioned cured product. In the article of this embodiment, the coating film can function as an insulating material with excellent heat resistance and coating appearance.

The article of the present embodiment is typically a printed wiring board or a substrate for a semiconductor package in which a solder resist film (the above-mentioned coating film) is formed at an appropriate position on the surface layer.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the Examples below. In the following, "parts" and "%" are based on mass unless otherwise specified.

The measurement conditions for gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), liquid chromatography mass spectrometry (LC-MS), and amine equivalent are as follows.

<Measurement conditions for gel permeation chromatography (GPC)>
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
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40℃
Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with 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 1.0% by mass tetrahydrofuran solution (calculated as solid content of the resin) filtered through a microfilter (50 μl) was used.

<Measurement conditions for high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS)>
Controller: Agilent Technologies 1260 Infinity II
Column: Agilent EC-C18 (4.6 x 50 mm, 2.7 μm)
Column temperature: 40℃
Pump flow rate: 1.0ml/min Elution conditions: K1-water, K2-acetonitrile
K1/K2=0/100 → 30/70 (linear concentration change 0-1.67 minutes)
K1/K2=30/70 (1.67-5 minutes)
K1/K2=30/70→90/10 (5-8 minutes)
(Ratio is volume ratio)
Detection wavelength: UV254, 275, 300nm
MS: Agilent Technologies InfinityLab LC/MSD

<Measurement of amine equivalent>
Approximately 2.5 g of a polyamine compound as a sample was placed in a 500 mL Erlenmeyer flask with a stopper, and 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed, a cooling tube was attached, and the temperature was heated to 120°C. The mixture was heated under reflux for 150 minutes in an oil bath set at .
After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed with a 0.5 mol/L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was performed and corrected in the same manner, and the amine equivalent was measured.
Amine equivalent (g/eq.)=(S×2,000)/(Blank-A)
S: Sample amount (g)
A: Consumption amount (mL) of 0.5 mol/L potassium hydroxide-ethanol solution
Blank: Consumption amount (mL) of 0.5 mol/L potassium hydroxide-ethanol solution in blank test

Furthermore, the evaluation methods for heat resistance and coating film appearance are as follows.

<Evaluation of heat resistance>
The resin composition obtained in each example and comparative example was applied onto a copper foil (manufactured by Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using an applicator to a film thickness of 50 μm, It was dried at 80°C for 30 minutes. Next, after irradiating with ultraviolet rays at 10 kJ/m ² using a metal halide lamp, the film was heated at 160° C. for 1 hour to obtain a cured coating film. Next, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm x 35 mm was cut out from this cured product, and measured using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Co., Ltd., tensile method: frequency 1Hz, heating rate 3°C/min). The temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature (°C). The higher the glass transition temperature (°C), the better the heat resistance.

<Evaluation of paint film appearance>
The resin compositions obtained in each example and comparative example were applied to a 125 μm PET film (“Cosmoshine A4300” manufactured by Toyobo Co., Ltd.) using a bar coater (#12) and dried at 80° C. for 5 minutes. Next, ultraviolet rays of 5 kJ/m ² were irradiated using a metal halide lamp to obtain a cured coating film with a thickness of 10 μm. The appearance of this coating film was visually evaluated according to the following criteria.
○: No cloudiness ×: Cloudiness

(Synthesis Example 1: Synthesis of maleimide resin (A-1))
In a 500 mL eggplant flask attached to a rotary evaporator, 52.40 g (0.43 mol) of 2,6-xylidine, 64.52 g (0.43 mol) of 2,6-diethylaniline, 22.14 g of distilled water, and p-toluenesulfonic acid. 22.73g was charged and heated to 70°C while stirring. After holding at 70° C. for 30 minutes, 34.98 g (0.43 mol) of a 37% formalin solution was added in 4 portions over 1 hour and reacted for 4 hours. After the reaction, the reaction solution was air-cooled to room temperature, transferred to a 2 L separable flask, and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of a 10% aqueous sodium hydroxide solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 109.48 g of polyamine compound (1). The amine equivalent of polyamine compound (1) was 146 g/eq.

78.35 g of polyamine compound (1) (0.54 mol in terms of amine equivalent), 231.5 g of toluene, and 23.3 g of dimethylformamide were placed in a 2 L flask equipped with a thermometer, cooling tube, Dean-Stark trap, and stirrer, and the mixture was heated to room temperature. It was stirred with 59.53 g (0.61 mol) of maleic anhydride was added in 4 portions over 1 hour, and the mixture was reacted for an additional 1 hour at room temperature. Add 2.3 g of p-toluenesulfonic acid monohydrate, heat the reaction solution, cool and separate the water and toluene that azeotropes under reflux, and then return only toluene to the system to continue the dehydration reaction. Time went. The solution, which was allowed to cool to 60° C., was washed twice with 100 g of a 5% aqueous sodium hydrogen carbonate solution and seven times with 150 g of distilled water. During the process, 200 g of toluene was added to improve the separation ability. The mixture was concentrated under reduced pressure to obtain 105.7 g of maleimide resin (A-1). Peaks at M+=432, 460, and 488 were confirmed in the LC-MS spectrum. Each peak corresponds to an ammonia adduct of the following compound (including maleimide compound (a)). Further, the content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC chart was 96%. A GPC chart of maleimide resin (A-1) is shown in FIG.

(Synthesis Example 2: Synthesis of maleimide resin (A-2))
In a 500 mL eggplant flask attached to a rotary evaporator, 52.11 g (0.43 mol) of 2-ethylaniline, 64.17 g (0.43 mol) of 2,6-diethylaniline, 22.14 g of distilled water, and 22 g of p-toluenesulfonic acid. .73g was charged and heated to 70°C while stirring. After holding at 70° C. for 30 minutes, 34.98 g (0.43 mol) of a 37% formalin solution was added in 4 portions over 1 hour and reacted for 4 hours. After the reaction, the reaction solution was air-cooled to room temperature, transferred to a 2 L separable flask, and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of a 10% aqueous sodium hydroxide solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 119.02 g of polyamine compound (2). The amine equivalent of polyamine compound (2) was 165 g/eq.

87.45 g of polyamine compound (2) (0.53 mol in terms of amine equivalent), 231.5 g of toluene, and 23.3 g of dimethylformamide were placed in a 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, and the mixture was heated to room temperature. It was stirred with 59.53 g (0.61 mol) of maleic anhydride was added in 4 portions over 1 hour, and the mixture was reacted for an additional 1 hour at room temperature. After adding 2.3 g of p-toluenesulfonic acid monohydrate, heating the reaction solution and cooling and separating the water and toluene that azeotroped under reflux, only toluene was returned to the system and the dehydration reaction was continued for 6 hrs. Time went. The solution, which was allowed to cool to 60° C., was washed twice with 100 g of a 5% aqueous sodium hydrogen carbonate solution and seven times with 150 g of distilled water. During the process, 200 g of toluene was added to improve the separation ability. The mixture was concentrated under reduced pressure to obtain 123.36 g of maleimide resin (A-2). Peaks at M+=432, 460, and 488 were confirmed in the LC-MS spectrum. Each peak corresponds to an ammonia adduct of the following compound (including maleimide compound (a)). Further, the content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC chart was 56%. A GPC chart of the maleimide resin (A-2) is shown in FIG.

(Synthesis Example 3: Synthesis of maleimide resin (A-3))
In a 500 mL eggplant flask attached to a rotary evaporator, 52.11 g (0.43 mol) of 2-ethylaniline, 52.11 g (0.43 mol) of 2,6-xylidine, 22.14 g of distilled water, and 22.0 g of p-toluenesulfonic acid were placed. 73 g was charged and heated to 70° C. with stirring. After holding at 70° C. for 30 minutes, 34.98 g (0.43 mol) of a 37% formalin solution was added in 4 portions over 1 hour and reacted for 4 hours. After the reaction, the reaction solution was air-cooled to room temperature, transferred to a 2 L separable flask, and diluted with 140 g of toluene. The diluted solution was washed once with 100 g of a 10% aqueous sodium hydroxide solution and four times with 100 g of distilled water, and concentrated under reduced pressure to obtain 106.11 g of polyamine compound (3). The amine equivalent of polyamine compound (3) was 147 g/eq.

77.91 g of polyamine compound (3) (0.53 mol in terms of amine equivalent), 231.5 g of toluene, and 23.3 g of dimethylformamide were placed in a 2 L flask equipped with a thermometer, cooling tube, Dean-Stark trap, and stirrer, and the mixture was heated to room temperature. It was stirred with 59.53 g (0.61 mol) of maleic anhydride was added in 4 portions over 1 hour, and the mixture was reacted for an additional 1 hour at room temperature. Add 2.3 g of p-toluenesulfonic acid monohydrate, heat the reaction solution, cool and separate the water and toluene that azeotropes under reflux, and then return only toluene to the system to continue the dehydration reaction. Time went. The solution, which was allowed to cool to 60° C., was washed twice with 100 g of a 5% aqueous sodium hydrogen carbonate solution and seven times with 150 g of distilled water. During the process, 200 g of toluene was added to improve the separation ability. The mixture was concentrated under reduced pressure to obtain 113.09 g of maleimide resin (A-3). A peak at M+=432 was confirmed in the LC-MS spectrum. The peak corresponds to an ammonia adduct of the following compound (including maleimide compound (a)). Further, the content of the binuclear component (bismaleimide compound) calculated from the area ratio of the GPC chart was 58%. A GPC chart of the maleimide resin (A-3) is shown in FIG.

(Synthesis Examples 4 to 6: Synthesis of maleimide resins (A-4) to (A-6))
Maleimide resins (A-4) to (A-6) were synthesized in the same manner as in Example 1, except that the type and amount (number of moles) of the aromatic monoamine compound were changed as shown in Table 1. GPC charts of maleimide resins (A-4) to (A-6) are shown in FIGS. 4 to 6, respectively. It was confirmed from the MS spectrum of each maleimide resin that each contained an asymmetric bismaleimide compound (maleimide compound (a)). Further, Table 1 shows the content of the binuclear component (bismaleimide compound) of each maleimide resin calculated from the area ratio of the GPC chart.

(Examples 1 to 6: Preparation of resin compositions (1) to (6))
The maleimide resin (A) obtained in the above synthesis example and the compound (B-1) having a polymerizable unsaturated group (acryloyl group) (oxyethylene (EO) modified diacrylate of bisphenol A (manufactured by Miwon Specialty Chemical Co., Ltd.) Miramaer M240") were mixed in the composition ratio shown in Table 2 to obtain a resin composition. To this resin composition, methyl ethyl ketone as an organic solvent and a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins) were added. ) and 2-ethyl-4-methylimidazole as a curing accelerator were mixed in the composition ratio shown in Table 2 to obtain resin compositions (1) to (6), respectively. ) to (6) were evaluated for heat resistance and coating appearance.The results are shown in Table 2.

(Comparative Example 1: Preparation of resin composition (C1))
Same as Example 1 above, except that 4,4'-diphenylmethane bismaleimide ("BMI-1000" manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used instead of the maleimide resin (A) obtained in the above synthesis example. The resin composition (C1) was obtained by mixing in the composition ratio shown in Table 2 in the same manner as described above. Note that 4,4'-diphenylmethane bismaleimide is a maleimide compound having two identical aromatic ring-maleimide skeletons. The resulting resin composition (C1) was evaluated for heat resistance and coating film appearance. The results are shown in Table 2.

Table 2 shows that the resin compositions of Examples can exhibit superior heat resistance and coating film appearance in the resulting cured products (cured coating films) compared to Comparative Examples.

According to the present invention, it is possible to provide a resin composition capable of obtaining a cured coating film having excellent heat resistance and coating film appearance. Further, according to the present invention, it is possible to provide a cured product obtained using the resin composition and an article using the cured product.

Claims (6)

A resin composition containing a maleimide resin (A) and a compound (B) having a polymerizable unsaturated group,
The maleimide resin (A) has the following general formula (1) in one molecule:

The first aromatic ring-maleimide skeleton represented by the following general formula (2):

A maleimide compound (a) having a second aromatic ring-maleimide skeleton represented by [where R ¹ to R ⁴ are each independently hydrogen or methyl] group or ethyl group, Ar ¹ and Ar ² each independently represent an aromatic ring which may have one or more substituents, and * represents a bond from the aromatic ring to another site. Ar ¹ and Ar ² differ from each other in at least one of the types of substituents, the number of substituents, and the positions of the substituents. The maleimide compound (a) is an asymmetric bis compound in which the first aromatic ring-maleimide skeleton and the second aromatic ring-maleimide skeleton are bonded via an organic group having 1 to 200 carbon atoms. The resin composition according to claim 1, which is a maleimide compound. According to claim 1 or 2, the solid content of the maleimide resin (A) is in the range of 1 to 10,000 parts by mass based on 100 parts by mass of the solid content of the compound (B) having a polymerizable unsaturated group. resin composition. The resin composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator. A cured product of the resin composition according to claim 4. An article comprising a coating film made of the cured product according to claim 5.

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