JP7433607B2 - Glass fiber-containing resin composition and cured product - Google Patents

Description

The present invention relates to a glass fiber-containing resin composition and a cured product obtained from the glass fiber-containing resin composition.

Thermosetting resin molding materials made of phenol resin, epoxy resin, benzoxazine resin, etc. reinforced with glass fiber are used for automobile engine peripheral parts, various electrical components, pump-related parts, etc. Particularly in recent years, the use of resins for metal parts has progressed, and there is a demand for materials and compositions that have further improved performance, typified by high heat resistance, high strength, and high rigidity, as well as materials and compositions that have all of these properties. Among these, bismaleimide (BMI) exhibits superior heat resistance (high glass transition temperature and high strength) compared to conventional epoxy resins and phenolic resins, so it has recently attracted attention as a resin material for metal replacement applications. ing.

In the market, BMI having a DDM (4,4'-diaminodiphenylmethane) or DDE (4,4'-diaminodiphenyl ether) skeleton is distributed as a highly heat-resistant resin (see, for example, Patent Document 1). However, BMI, which has high heat resistance, has a high melting point, so the melting point and hardening start temperature are close to each other, making it difficult to melt and knead glass fiber at a low temperature where hardening does not proceed, so it can only be used in limited applications. In addition to the problems, adhesion to glass fibers is low, and further improvements and performance improvements are strongly desired.

Japanese Patent Application Publication No. 2015-193628

The object of the present invention is to provide a (meth)allyl group-containing maleimide compound having a specific structure, a hydroxyl group-containing maleimide compound having a specific structure, and a specific resin composition that can yield a cured product with excellent heat resistance and mechanical strength. The object of the present invention is to provide a glass fiber-containing resin composition containing glass fibers coated with a material, a cured product obtained by curing the glass fiber-containing resin composition, and the like.

As a result of intensive studies, the present inventors found that a (meth)allyl group-containing maleimide compound having a specific structure, a hydroxyl group-containing maleimide compound having a specific structure, and a glass containing glass fibers coated with a specific resin composition. It has been discovered that a fiber-containing resin composition solves the above problems.

（上記式（１）中、ｎ_１及びｍ_１はそれぞれ独立して１～５の整数であって、Ａｌｙは下記式（２）で表される（メタ）アリル基を有する基であって、ＭＩは下記式（３）で表されるマレイミド基を有する基であって、Ａ_１はベンゼン環を１個以上有する構造である。）

（上記式（２）中、Ｚ_１は直接結合または置換基を有していても良い炭素数１～１０の炭化水素基であって、Ｒ^１は水素原子またはメチル基を表す。）

（上記式（３）中、Ｚ_２は直接結合または置換基を有していても良い炭素数１または２の炭化水素基であって、Ｒ^２及びＲ^３はそれぞれ独立して水素原子またはメチル基を表す。）

（上記式（４）中、ｎ_２及びｍ_２はそれぞれ独立して１～５の整数であって、ＭＩは上記式（３）で表されるマレイミド基を有する基であって、Ａ_２はベンゼン環を１個以上有する構造である。） That is, the present invention provides a (meth)allyl group-containing maleimide compound represented by the following formula (1), a hydroxyl group-containing maleimide compound represented by the following formula (4), and a polymerizable double bond concentration of 3 mol%. The present invention relates to a glass fiber-containing resin composition containing glass fibers coated with a resin composition containing at least one of a polyester resin and a polyurethane resin.

(In the above formula (1), n ₁ and m ₁ are each independently an integer of 1 to 5, and Aly is a group having a (meth)allyl group represented by the following formula (2), MI is a group having a maleimide group represented by the following formula (3), and _A1 is a structure having one or more benzene rings.)

(In the above formula (2), Z ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent, and R ¹ represents a hydrogen atom or a methyl group.)

(In the above formula (3), Z ₂ is a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent, and R ² and R ³ are each independently a hydrogen atom or a methyl (Represents a group.)

(In the above formula (4), n ₂ and m ₂ are each independently an integer of 1 to 5, MI is a group having a maleimide group represented by the above formula (3), and A ₂ is It is a structure with one or more benzene rings.)

In the glass fiber-containing resin composition of the present invention, in the above formula (1), A ₁ preferably has one of the structures represented by the following formula (5).

In the glass fiber-containing resin composition of the present invention, preferably, in the above formula (4), A ₂ is a benzene ring structure, and n ₂ and m ₂ are both 1.

It is preferable that the glass fiber-containing resin composition of the present invention further contains an epoxy compound.

The present invention relates to a compound containing the glass fiber-containing resin composition.

The present invention relates to a cured product obtained by curing the glass fiber-containing resin composition.

The present invention relates to a composition for heat-resistant materials containing the glass fiber-containing resin composition.

The present invention relates to a heat-resistant member containing the cured product.

According to the present invention, the obtained cured product has excellent heat resistance and mechanical strength, and can also be suitably used for compounds, heat-resistant members, etc. using the glass fiber-containing resin composition.

The present invention relates to a (meth)allyl group-containing maleimide compound having a structure having one or more benzene rings, one or more groups having a (meth)allyl group, and further having one or more groups having a maleimide group. and a hydroxyl group-containing maleimide compound having a structure having one or more benzene rings, one or more groups having a hydroxyl group, and further having one or more maleimide groups, and a polymerizable double bond concentration of 3 mol%. The present invention provides a glass fiber-containing resin composition containing glass fibers coated with a resin composition containing at least one of a polyester resin and a polyurethane resin.

<(Meth)allyl group-containing maleimide compound>
The (meth)allyl group-containing maleimide compound of the present invention has a structure having one or more benzene rings, has one or more groups having a (meth)allyl group, and further has one or more groups having a maleimide group. It is a compound represented by the following formula (1), which is characterized by having:

In the above formula (1), n ₁ and m ₁ are each independently an integer of 1 to 5, Aly is a group having a (meth)allyl group represented by the following formula (2), and MI is a group having a maleimide group represented by the following formula (3), and A ₁ is a structure having one or more benzene rings.

In the above formula (2), Z ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent, and R ¹ represents a hydrogen atom or a methyl group.

In the above formula (3), Z ₂ is a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent, and R ² and R ³ are each independently a hydrogen atom or a methyl group. represents.

Here, the (meth)allyl group-containing maleimide compound has one or more benzene rings, thereby improving heat resistance, particularly heat resistance to decomposition temperature. Furthermore, since the presence of a maleimide group increases the glass transition temperature, the heat resistance is further improved. Moreover, since the (meth)allyl group improves reactivity and lowers the melting point, handling properties are improved and it can be suitably used in various applications.

Here, the (meth)allyl group-containing maleimide compound has a structure in which A ₁ in the above formula (1) has one or more benzene rings. An example of a structure having one or more benzene rings is a structure represented by the following formula (6).

In the above structure, the benzene ring may or may not have a substituent, and there is no particular limitation on the bonding method of the substituent. In addition, when multiple benzene rings exist, the benzene rings may be bonded directly to each other, may be bonded to each other through a linking group, or may be fused to each other to form a condensed ring. I don't mind.
X in the above formula (6) represents a direct bond or a divalent linking group. Examples of the divalent linking group include a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent, an oxygen atom, a carbonyl group, a sulfur atom, a sulfone group, and a divalent alicyclic structure.
Y in the above formula (6) represents a trivalent linking group. Examples of the trivalent linking group include a hydrocarbon group having 1 to 3 carbon atoms having a substituent, a nitrogen atom, and a trivalent alicyclic structure.

Among the structures having one or more benzene rings represented by the above formula (6), preferred structures include any of the structures represented by the following formula (5).

In the above formula (6), the hydrogen atom of the benzene ring structure may be replaced with a substituent as long as the effects of the present invention are not impaired. Examples of the substituent include known and commonly used substituents. For example, a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a halogen atom, a hydroxyl group, an amino group, an amide group, a ureido group, a urethane group, a carboxyl group, an alkoxy group, a thioether group, an acyl group, Examples include acyloxy group, alkoxycarbonyl group, cyano group, and nitro group.

In the above formula (1), n ₁ may be an integer of 1 to 5, and it is preferable that n ₁ is 2 or more because it lowers the melting point. Further, m ₁ may be an integer of 1 to 5, and it is preferable that m ₁ is 2 or more because heat resistance is improved.
The ratio of m ₁ and n ₁ may be m ₁ :n ₁ =1:5 to 5:1. It is particularly preferable that m ₁ :n ₁ =1:2 to 2:1, since both heat resistance and low melting point can be achieved.
There is no particular limitation on the bonding location of the group containing a (meth)allyl group and the group containing a maleimide group, but if the group containing a maleimide group and the group containing a (meth)allyl group exist on the same benzene ring, , is preferable because the heat resistance is further improved.

In the above formula (2), Z ₁ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent. Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, an aralkylene group, and a combination of two or more thereof. Examples of the alkylene group include a methylene group, a methine group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkenylene group include vinylene group, 1-methylvinylene group, propenylene group, butenylene group, and pentenylene group. Examples of the alkynylene group include ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, and the like. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Examples of the arylene group include a phenylene group, tolylene group, xylylene group, and naphthylene group.

In the above formula (2), preferable structures for Z ₁ include a direct bond or a methylene group.

In the above formula (3), Z ₂ represents a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent. Preferably it is a direct bond or a methylene group.

Particularly preferred structures of the (meth)allyl group-containing maleimide compound of the present invention are structures exemplified by the following formulas (7-1) to (7-14).

Among the above formulas (7-1) to (7-14), the above formulas (7-1), (7-2), (7-3), (7-4), and (7- 5), (7-6), (7-8), (7-12), and (7-13). It is preferable that a group containing a (meth)allyl group and a maleimide group exist in the same benzene ring because the melting point tends to decrease. Further, when cured, heat resistance is improved, which is preferable.

<Production (synthesis) method of (meth)allyl group-containing maleimide compound>
Although the method for producing the (meth)allyl group-containing maleimide compound of the present invention is not particularly limited, it can be efficiently produced through the following steps.

<Manufacturing method 1>
1-1) Step of protecting the amino group of a hydroxyl group-containing aromatic amino compound having a benzene ring 1-2) Step of (meth)allylating the hydroxyl group of the compound obtained in 1-1) 1-3) 1- Step of deprotecting the protected amino group of the compound obtained in 2) 1-4) Step of converting the amino group of the compound obtained in step 1-3 into maleimidation

By using a hydroxyl group-containing aromatic amino compound having a benzene ring, it has a structure having one or more benzene rings of the present invention, has one or more groups having a (meth)allyl group, and further has one maleimide group. It is possible to produce a (meth)allyl group-containing maleimide compound, which is characterized by having at least one (meth)allyl group.

In the above formula (8), n ₁ and m ₁ are each independently an integer of 1 to 5, Aly is a group having a (meth)allyl group represented by the following formula (2), and B ₁ is a group having an amino group represented by the following formula (9), and A ₁ is a structure having one or more benzene rings.

Preferably, the hydroxyl group-containing aromatic amino compound having a benzene ring includes a compound having one of the structures represented by the above formula (8), a hydroxyl group, and an amino group. Specifically, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino -4-hydroxyphenyl) sulfone, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 9,9-bis(3-amino-4- Examples include conventionally known compounds such as hydroxyphenyl)fluorene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, and 4,4'-diamino-4''-hydroxytriphenylamine, but are limited to these. Any phenol compound having an amino group may be used.
A method for producing an aromatic aminophenol compound includes a method in which a hydroxyl group-containing aromatic compound is nitrated and then reduced.

In the above formula (2), Z ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent, and R ¹ represents a hydrogen atom or a methyl group.

In the above formula (9), Z ₂ represents a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent.

The amino group in step 1-1) may be protected by any known and commonly used method, for example, by acetylation. For acetylation, any known and commonly used acetylating agent may be used, such as acetic anhydride, acetyl chloride, and the like.

In step 1-2), for example, the hydroxyl group of the hydroxyl group-containing aromatic amino compound in which the amino group is protected is reacted with a halogenated (meth)allyl compound in the presence of a base to (meth)allylate it. I can do it. Examples of the halogenated (meth)allyl compound include (meth)allyl bromide and (meth)allyl chloride, and examples of the base include potassium carbonate.

In step 1-3) and step 1-4), the protected amino group is deprotected and the amino group is converted into maleimide. The amino group can be converted into maleimidation by, for example, reacting with a compound represented by the following formula (10).

In the above formula (10), R ² and R ³ each independently represent a hydrogen atom or a methyl group.

Examples of the compound represented by the above formula (10) include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and the like.

By going through the above steps, a compound having a structure having one or more benzene rings of the present invention, having one or more groups having a (meth)allyl group, and further having one or more groups having a maleimide group can be obtained. A (meth)allyl group-containing maleimide compound having certain characteristics can be produced.

When synthesizing the (meth)allyl group-containing maleimide compound, unreacted monomers may remain in the reaction product, or other compounds different from the (meth)allyl group-containing maleimide compound may be produced as a product. Examples of other compounds include unclosed amic acids, isoimides, monomers, and product oligomers. Substances other than these (meth)allyl group-containing maleimide compounds may be removed through a purification step, or may be used as they are contained depending on the purpose.

<Hydroxy group-containing maleimide compound>
In addition to the (meth)allyl group-containing maleimide compound, the glass fiber-containing resin composition of the present invention has a structure having one or more benzene rings, one or more groups having a hydroxyl group, and further contains a maleimide group. Contains a hydroxyl group-containing maleimide compound represented by the following formula (4), which is characterized by having one or more of the following.

In the above formula (4), n ₂ and m ₂ are each independently an integer of 1 to 5, MI is a group having a maleimide group represented by the above formula (3), and A ₂ is benzene. It is a structure having one or more rings. )

The glass fiber-containing resin composition of the present invention improves adhesion to glass fibers by containing both a (meth)allyl group-containing maleimide compound and a hydroxyl group-containing maleimide compound. Moreover, since the hydroxyl group-containing maleimide compound of the present invention has an aromatic ring structure, the glass fiber-containing resin composition containing it has high heat resistance.

In the above formula (4), n ₂ may be an integer of 1 to 5, and m ₂ may be an integer of 1 to 5.
The ratio of m ₂ and n ₂ may be m ₂ :n ₂ =1:5 to 5:1. It is particularly preferable that m ₂ :n ₂ =1:2 to 2:1, since both heat resistance and low melting point can be achieved.
Although there is no particular limitation on the bonding location between the hydroxyl group and the maleimide group, it is preferable that the maleimide group and the group containing the hydroxyl group exist on the same benzene ring because heat resistance is further improved.

A particularly preferred structure of the hydroxyl group-containing maleimide compound of the present invention is the structure of the following formula (11), in which A ₂ is a benzene ring structure, and n ₂ and m ₂ are both 1.

<Production (synthesis) method of hydroxyl group-containing maleimide compound>

The method for producing a hydroxyl group-containing maleimide compound of the present invention is not particularly limited, but by maleimidizing a hydroxyl group-containing aromatic amino compound having a benzene ring, it has a structure having one or more benzene rings of the present invention, It is possible to produce a hydroxyl group-containing maleimide compound characterized by having one or more groups having a hydroxyl group and further having one or more maleimide groups.

Preferably, the hydroxyl group-containing aromatic amino compound having a benzene ring includes a compound having one of the structures represented by the above formula (6), a hydroxyl group, and an amino group. Specifically, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2,4-dihydroxyaniline, 2,6-dihydroxyaniline, 2,2-bis(3-amino-4-hydroxyphenyl)propane , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)sulfone, 4,4'-diamino-3,3'-dihydroxy Biphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene , 4,4'-diamino-4''-hydroxytriphenylamine and the like, but the present invention is not limited thereto, and any phenol compound having an amino group may be used.
A method for producing an aromatic aminophenol compound includes a method in which a hydroxyl group-containing aromatic compound is nitrated and then reduced.

The amino group can be converted into maleimidation by, for example, reacting with a compound represented by the above formula (10).

Examples of the compound represented by the above formula (10) include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and the like.

By going through the above steps, the hydroxyl group-containing maleimide of the present invention, which has a structure having one or more benzene rings, has one or more groups having a hydroxyl group, and further has one or more maleimide groups, can be obtained. Compounds can be manufactured.

When synthesizing the hydroxyl group-containing maleimide compound of the present invention, unreacted monomers may remain in the reaction product, or other compounds different from the hydroxyl group-containing maleimide compound may be produced as a product. Examples of other compounds include unclosed amic acids, isoimides, monomers, and product oligomers. Substances other than these hydroxyl group-containing maleimide compounds may be removed through a purification step, or may be used as they are, depending on the purpose.

In the glass fiber-containing resin composition of the present invention, the blending ratio (mass ratio) of the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound may be appropriately adjusted and used within a range that does not impair the effects of the present invention. Preferably, the ratio of the (meth)allyl group-containing maleimide compound of the present invention to the hydroxyl group-containing maleimide compound is 1:5 to 5:1. This is because within this range, the balance between heat resistance and adhesion is excellent. Particularly preferred is 1:2 to 4:1.

<Glass fiber>
The glass fiber-containing resin composition of the present invention contains glass fibers coated with a resin composition containing at least one of a polyester resin and a polyurethane resin and having a polymerizable double bond concentration of 3 mol% or more. It is characterized by The resin composition is useful because it functions as a fiber sizing agent and can yield a cured product that has excellent glass fiber sizing properties and excellent mechanical strength.

In addition to the glass fibers described above, other fibrous substrates can be used in the glass fiber-containing resin composition of the present invention. The fibrous substrate is not particularly limited, but those used in fiber-reinforced resins are preferred, and examples include inorganic fibers and organic fibers.

Examples of the inorganic fiber include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, tungsten carbide fiber, silicon carbide fiber (silicon carbide fiber), Examples include ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers. Among these, only one type may be used, or a plurality of types may be used simultaneously.

The organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, cellulose, and pulp. , natural fibers such as cotton, wool, and silk, and recycled fibers such as proteins, polypeptides, and alginic acid. Among them, carbon fibers and glass fibers are preferred because they have a wide range of industrial applications. Among these, only one type may be used, or a plurality of types may be used simultaneously.

The glass fibers used in the present invention may be an aggregate of fibers, may be continuous or discontinuous, and may be woven or non-woven. . Further, it may be a fiber bundle in which the fibers are aligned in one direction, or it may be in the form of a sheet in which the fiber bundles are arranged. Further, the fiber aggregate may have a three-dimensional shape with a thickness.

The glass fibers are not particularly limited, and include, for example, long glass fibers and short glass fibers. Note that this classification method is based on the manufacturing method, so even fibers cut into short lengths of about 3 mm, such as chopped strands, are called long glass fibers.

The polyester resin is not particularly limited, but can be obtained by, for example, reacting diols such as neopentyl glycol, polypropylene glycol, polycaprolactone ester polyol, and polybutadiene with hydroxyl groups at both ends with maleic anhydride, butyrolactone, benzoic acid, etc. It will be done.

The polyurethane resin is not particularly limited, but can be obtained by, for example, reacting isocyanates such as xylene diisocyanate and isophorone diisocyanate with polycaprolactone ester polyol, polybutadiene with hydroxyl groups at both ends, neopentyl glycol, polypropylene glycol, and the like.

When the resin composition contains at least one of a polyester resin and a polyurethane resin, the concentration of polymerizable double bonds is 3 mol% or more, preferably 5 mol% or more, and more preferably , 5 to 35 mol%, more preferably 5 to 25 mol%. When the polymerizable double bond concentration is 3 mol % or more, the wettability and adhesion to glass fibers become good, and the fiber dispersibility in the compound becomes a preferable aspect.

The glass fiber-containing resin composition may optionally contain a silane coupling agent, a curing catalyst, a lubricant, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, and an optical brightener. , additives such as foaming agents, pH adjusters, leveling agents, anti-gelling agents, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparters, inorganic fillers, organic fillers, plasticizers, reinforcing agents , catalyst, antibacterial agent, antifungal agent, rust preventive agent, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam crystal water-containing compounds, flame retardants, water absorbing agents, moisture absorbing agents, deodorizing agents, foam stabilizers, antifoaming agents, antifungal agents, preservatives, algaecides, pigment dispersants, antiblocking agents, hydrolysis prevention Agents etc. can be used in combination.

<Glass fiber-containing resin composition>
The glass fiber-containing resin composition of the present invention comprises a polyester resin and a polyurethane resin containing the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, and the polymerizable double bond concentration of 3 mol% or more. It is characterized by containing glass fibers coated with a resin composition containing at least one of them. The cured product obtained by curing the glass fiber-containing resin composition has excellent heat decomposition resistance, a high glass transition temperature, and low linear expansion, and can therefore be suitably used for heat-resistant members.

<Production (preparation) method of glass fiber-containing resin composition>
A resin composition containing at least one of a polyester resin and a polyurethane resin, the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, and the polymerizable double bond concentration of 3 mol% or more. The method for manufacturing (preparing) the glass fiber-containing resin composition containing the coated glass fiber is not particularly limited, but a simple method is to use the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, Then, the glass fibers coated with the resin composition may be mixed as they are.

In order to mix the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound more uniformly, the (meth)allyl group-containing maleimide compound represented by the above formula (1) and the above formula (4) are combined. a step of preparing a mixed solution (i) by mixing the hydroxyl group-containing maleimide compound and a solvent;
The mixed solution (i) is further mixed with glass fibers coated with a resin composition containing at least one of a polyester resin and a polyurethane resin, which contains the polymerizable double bond concentration of 3 mol% or more. A step of preparing a mixed solution (ii);
A uniform glass fiber-containing resin composition can be produced by a production method that includes the step of removing the solvent from the glass fiber-containing mixed liquid (ii). As a result, the two types of maleimide compounds are dispersed at the molecular level, and the glass fibers are also uniformly dispersed in the mixed liquid, making it possible to lower the viscosity of the glass fiber-containing resin composition.

In order to produce the mixed solution (i), the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound may be mixed by dissolving them in one solvent.
Alternatively, the method may be such that the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound are individually dissolved in a solvent, and then the solutions are mixed together. At this time, the solvents for dissolving each of the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound may be different solvents as long as they are compatible, and of course the same solvent may be used.
Furthermore, in order to mix the glass fiber coated with a resin composition containing at least one of a polyester resin and a polyurethane resin and having a polymerizable double bond concentration of 3 mol% or more, a coupling agent and a releasing agent are added. A molding agent etc. can also be used.

Examples of solvents that can be used in preparing the mixtures (i) and (ii) include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), and cyclic solvents such as tetrahydrofuran (THF) and dioxolane. These include ethers, esters such as methyl acetate, ethyl acetate, and butyl acetate, aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. Although they can be used alone or in combination, ethyl acetate, methyl ethyl ketone, and toluene are preferred from the viewpoint of solubility of the glass fiber-containing resin composition, volatility during solvent distillation, and solvent recovery.

The glass fiber-containing resin composition can also be produced by mixing the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound precursor, and then converting the mixture into maleimide all at once. be able to. By using this method, the manufacturing (synthesis) process can be simplified, and the two types of maleimide compounds can be dispersed at the molecular level, making it possible to reduce the viscosity of the compound.

Specifically, a (meth)allyl group-containing amino compound represented by the following formula (8) and a hydroxyl group-containing amino compound represented by the following formula (12) are mixed to produce an aromatic amino compound mixture. The process of
A composition containing a (meth)allyl group-containing compound and a hydroxyl group-containing maleimide compound can be produced all at once by a production method that includes a step of maleimidizing an aromatic amino compound mixture.

In the above formula (8), n ₁ and m ₁ are each independently an integer of 1 to 5, Aly is a group having a (meth)allyl group represented by the following formula (2), and B ₁ is a group having an amino group represented by the following formula (9), and A ₁ is a structure having one or more benzene rings.

In the above formula (2), Z ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent, and R ¹ represents a hydrogen atom or a methyl group.

In the above formula (9), Z ₂ represents a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent.

In the above formula (12), n ₂ and m ₂ are each independently an integer of 1 to 5, B ₂ is a group having a maleimide group represented by the above formula (3), and A ₂ is It has a structure having one or more benzene rings.

<Epoxy compound>
The glass fiber-containing resin composition of the present invention may further contain an epoxy compound. By containing an epoxy compound, the adhesion to glass fibers is further improved. Further, the epoxy group of the epoxy compound and the hydroxyl group of the hydroxyl group-containing maleimide compound react, and furthermore, the maleimide groups of the (meth)allyl group-containing maleimide compound and the hydroxyl group-containing maleimide compound react with each other to form a composite crosslinked system. Therefore, heat resistance and low linear expansion properties are further improved.

When the glass fiber-containing resin composition of the present invention contains an epoxy compound, the blending ratio of the hydroxyl group-containing maleimide compound and the epoxy compound is 1:2 to 2:1 as the ratio of the hydroxyl group equivalent to the epoxy equivalent of the hydroxyl group-containing maleimide compound. is preferable from the viewpoint of curability and heat resistance. Particularly preferred is 1:1.5 to 1.5:1.

Examples of the epoxy compound include epoxy resin and phenoxy resin. The epoxy resin is not particularly limited as long as it has an epoxy group, and examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, bisphenol sulfide epoxy resin, Phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Phenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol cocondensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl-modified novolac type epoxy resins, anthracene type epoxy resins, and the like. Each of these may be used alone, or two or more types may be used in combination.

Phenoxy resin refers to a high molecular weight thermoplastic polyether resin based on diphenol and epihalohydrin such as epichlorohydrin, and preferably has a weight average molecular weight of 20,000 to 100,000. The structure of the phenoxy resin includes, for example, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenolacetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, Examples include those having one or more types of skeletons selected from terpene skeletons and trimethylcyclohexane skeletons.

Among the epoxy compounds, aromatic epoxy compounds are preferred, and polycyclic aromatic epoxy compounds having a plurality of aromatic rings are more preferred.
A preferred epoxy compound includes a structure represented by the following formula (13).

（上記式（１３）中のｒは繰り返し単位の平均で１～１０である。）

(r in the above formula (13) is 1 to 10 on average of the repeating units.)

<Filler>
The glass fiber-containing resin composition of the present invention may further contain a filler. Examples of fillers include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

Examples of inorganic fine particles with excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous powder) Examples of materials with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; materials with excellent conductivity include single metals or alloys ( For example, metal fillers and/or metal-coated fillers using iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.; Examples of materials with excellent barrier properties include mica, clay, kaolin, Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; materials with a high refractive index Examples include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, Photocatalytic metals such as silver, molybdenum, strontium, chromium, barium, and lead, composites of the above metals, and their oxides; those with excellent wear resistance include metals such as silica, alumina, zirconia, and magnesium oxide; Compounds and oxides of these materials; those with excellent conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; those with excellent insulation properties include silica; those with excellent ultraviolet shielding properties include: Titanium oxide, zinc oxide, etc.
These inorganic fine particles may be appropriately selected depending on the intended use, and may be used alone or in combination. Moreover, since the above-mentioned inorganic fine particles have various properties other than those listed in the examples, they may be selected depending on the application at the appropriate time.

For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Kogyo Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
In addition, commercially available colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, Examples include ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, and the like.

Surface-modified silica fine particles may be used; for example, the silica fine particles may be surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. can give. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd.; commercially available colloidal silica modified with a compound having a (meth)acryloyl group include: Examples include MIBK-SD manufactured by Nissan Chemical Industries, Ltd.

The shape of the silica fine particles is not particularly limited, and may be spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped. Further, the primary particle diameter is preferably in the range of 5 to 200 nm. If the diameter is less than 5 nm, the inorganic fine particles in the dispersion will not be sufficiently dispersed, and if the diameter exceeds 200 nm, the cured product may not maintain sufficient strength.

As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, such as anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, and the like. Furthermore, particles designed to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used. As the element to be doped into titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cation elements such as chromium, iron, cobalt, and manganese are suitably used. Moreover, as for the form, a powder, a sol or a slurry dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd. Furthermore, examples of commercially available slurry-like titanium oxide fine particles include TKD-701 manufactured by Teika Corporation.

<Reactive compound>
The glass fiber-containing resin composition of the present invention includes at least one of a polyester resin and a polyurethane resin containing the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, and the polymerizable double bond concentration of 3 mol% or more. The glass fiber coated with a resin composition containing one of the above-mentioned epoxy compounds may further contain a reactive compound in addition to the above-mentioned epoxy compound. By adding reactive compounds, it is possible to impart various characteristics to the resin, such as reactivity, heat resistance, and handling properties.
The reactive compound referred to here is a compound having a reactive group, and may be a monomer, oligomer, or polymer.

The reactive group may be a functional group that does not react with the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, or the above-mentioned epoxy compound, or a functional group that does, but in order to further improve heat resistance, , the (meth)allyl group-containing maleimide compound, the hydroxyl group-containing maleimide compound, and the above-mentioned epoxy compound. Examples include a cyanato group, a maleimide group, a phenolic hydroxyl group, an oxazine ring, an amino group, and a group having a carbon-carbon double bond.

Examples of compounds having a cyanato group include cyanate ester resins.
Examples of the compound having a maleimide group (maleimide compound) include maleimide resin and bismaleimide resin.
Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, cresol novolak resin, dicyclopentadiene-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, and biphenylaralkyl resin.
Examples of compounds having an oxazine ring (oxazine compounds) include benzoxazines obtained by reacting phenol compounds and aromatic amino compounds with formaldehyde. These phenol compounds and aromatic amino compounds may have a reactive functional group in their structure.
Examples of compounds having an amino group include DDM (4,4'-diaminodiphenylmethane), DDE (4,4'-diaminodiphenyl ether), 3,4'-diaminodiphenyl ether, 2,2-{bis4-(4-aminophenoxy ) phenyl}propane, 4,4'-bis(4-aminophenoxy)biphenyl, and other aromatic amino compounds.
Examples of the compound having a group having a carbon-carbon double bond include maleimide compounds, vinyl compounds, (meth)allyl compounds, and the like.

The above-mentioned reactive compound may have only one type of reactive group, or may have multiple types of reactive groups, and the number of functional groups may be one or more. Moreover, multiple types may be used at the same time.

Preferred reactive compounds include cyanate ester resins, maleimide compounds, vinyl compounds, and aromatic amino compounds. Particularly preferred among these are maleimide compounds, cyanate ester resins, and aromatic amino compounds.

The maleimide compound has an improved crosslinking density due to the self-addition reaction between the (meth)allyl group-containing maleimide compound and the maleimide groups, or the ene reaction between the allyl group and the maleimide group, resulting in improved heat resistance, especially glass transition temperature. improves.
Usually, in order to obtain a uniformly cured product using a maleimide compound, high temperature and long curing conditions are required, so in many cases, a peroxide catalyst is used in combination to promote the reaction. However, even when the (meth)allyl group-containing maleimide compound does not use a catalyst, the curing reaction proceeds and a uniform cured product can be obtained. The use of peroxide-based catalysts causes problems such as an increase in the viscosity of the composition, a decrease in pot life, and a decrease in physical properties due to trace amounts of peroxide remaining in the cured product. Since the meth)allyl group-containing maleimide compound does not require the use of a peroxide curing agent, these problems can be solved.

A cured product of a cyanate ester resin and the (meth)allyl group-containing maleimide compound exhibits excellent dielectric properties.

Aromatic amino compounds have improved crosslinking density and improved thermal decomposition temperature and glass transition temperature due to the Michael addition reaction between amino groups and maleimide groups.

Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, Naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin Resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol condensed novolac type Examples include cyanate ester resin, naphthol-cresol cocondensed novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, anthracene type cyanate ester resin. Each of these may be used alone, or two or more types may be used in combination.

Among these cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins, bisphenol E type cyanate ester resins, and polyhydroxynaphthalene type cyanate ester resins are preferred in that they yield cured products with particularly excellent heat resistance. It is preferable to use a naphthylene ether type cyanate ester resin, or a novolac type cyanate ester resin, and a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Examples of maleimide compounds include various compounds represented by any of the following structural formulas (i) to (iii).

R in the above formula (i) is an m-valent organic group, α and β are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and s is an integer of 1 or more.

R in the above formula (ii) is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, s is an integer from 1 to 3, and t is an average of 0 repeating units. ~10.

R in the above formula (iii) is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, s is an integer from 1 to 3, and t is an average of 0 repeating units. ~10. Each of these may be used alone, or two or more types may be used in combination.

The oxazine compound is not particularly limited, but for example, the reaction product of bisphenol F, formalin, and aniline (Fa-type benzoxazine resin), the reaction product of 4,4'-diaminodiphenylmethane, formalin, and phenol (P -d-type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition type resin and Examples include reaction products of formalin and aniline, reaction products of phenolphthalein, formalin and aniline, and reaction products of dihydroxydiphenyl sulfide, formalin and aniline. Each of these may be used alone, or two or more types may be used in combination.

Examples of vinyl compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, - Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as ethylhexyl (meth)acrylate and lauryl (meth)acrylate; aralkyl such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate (Meth)acrylates; Cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate (Meth)acrylates; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; Alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethyl malate, di- Dialkyl esters of unsaturated dibasic acids such as n-butyl maleate, dimethyl fumarate, and dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. fluoroolefins; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N,N-dimethyl (meth)acrylamide, N-(meth)acryloylmorpholine, N- Examples include tertiary amide group-containing monomers such as (meth)acryloylpyrrolidine and N-vinylpyrrolidone.

Examples of (meth)allylic compounds include allyl esters such as allyl acetate, allyl chloride, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate. ; Allyloxy alcohols such as allyloxymethanol and allyloxyethanol; diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, bisphenol A diallyl ether, Compounds containing two allyl groups such as bisphenol F diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether; triallyl isocyanate Examples include compounds containing three or more allyl groups such as nurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether, etc., or metaallylic forms of these compounds.

Both maleimide groups and (meth)allyl groups are present in the glass fiber-containing resin composition of the present invention. The ratio of maleimide group to (meth)allyl group is not particularly limited, but the number of moles of maleimide group: the number of moles of (meth)allyl group is preferably 1:10 to 10:1, and preferably 1:5 to 5:1. It is preferable because it has excellent heat resistance. In particular, a ratio of 1:2 to 3:1 is preferred because it provides an excellent balance between heat resistance and composition viscosity.

<Dispersion medium>
A dispersion medium may be used in the glass fiber-containing resin composition of the present invention for the purpose of adjusting the solid content and viscosity of the composition. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and includes various organic solvents, liquid organic polymers, and the like.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF), and dioxolane, and esters such as methyl acetate, ethyl acetate, and butyl acetate. , aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether.These can be used alone or in combination, but among them, methyl ethyl ketone is It is preferable from the viewpoint of volatility during processing and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, such as carboxyl group-containing polymer modified products (Floren G-900, NC-500: Kyoei-sha), acrylic polymers (Floren WK-20: Kyoei-sha). , a special modified phosphoric acid ester amine salt (HIPLAAD ED-251: Kusumoto Kasei), a modified acrylic block copolymer (DISPERBYK2000: BYK-CHEMIE), and the like.

<Resin>
Moreover, the glass fiber-containing resin composition of the present invention may contain resins other than the various compounds mentioned above. As the resin, any known and commonly used resin may be blended as long as it does not impair the effects of the present invention, and for example, thermosetting resins and thermoplastic resins can be used.

A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means such as heating, radiation, or a catalyst. Specific examples include phenolic resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin. Examples include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene-maleic anhydride (SMA) resins, and maleimide resins other than the allyl group-containing maleimide compound obtained by the present invention. It will be done. These thermosetting resins can be used alone or in combination of two or more.

Thermoplastic resin refers to resin that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndication Examples include tactic polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

<Curing agent>
The glass fiber-containing resin composition of the present invention may contain a curing agent depending on the formulation. For example, when a compound having an epoxy group (epoxy compound) is blended, an amine curing agent, an amide curing agent, etc. Various curing agents such as curing agents, acid anhydride curing agents, phenol curing agents, active ester curing agents, carboxyl group-containing curing agents, and thiol curing agents may be used in combination.

Amine-based curing agents include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenediamine, paraxylenediamine, diethyltoluenediamine, diethylenetriamine, triethylenetetramine, Examples include isophorone diamine, imidazole, BF3-amine complex, guanidine derivative, guanamine derivative and the like.

Examples of the amide curing agent include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid, and ethylenediamine, and the like.

Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples include hydrophthalic anhydride.

Examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4',4''-trihydroxytriphenylmethane, naphthalene diol, 1 , 1,2,2-tetrakis(4-hydroxyphenyl)ethane, calixarene, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyrock) resin), polyhydric phenol novolak resin synthesized from polyhydric hydroxy compounds represented by resorcinol novolak resin and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol cocondensation Novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol cores linked by bismethylene groups), biphenyl-modified naphthol resin (polyhydric naphthol compound with phenol nuclei linked by bismethylene groups) , aminotriazine-modified phenolic resin (a polyhydric phenol compound in which a phenol nucleus is linked with melamine, benzoguanamine, etc.) and an alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde) Examples include polyhydric phenol compounds such as compound).
These curing agents may be used alone or in combination of two or more types.

Further, when the glass fiber-containing resin composition of the present invention contains a compound having an epoxy group (epoxy compound), a curing accelerator can be used alone or in combination with the above-mentioned curing agent. Various compounds that promote the curing reaction of the epoxy resin can be used as the curing accelerator, such as phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts. Among these, it is preferable to use imidazole compounds, phosphorus compounds, and tertiary amine compounds. Among them, imidazole compounds are 2-ethyl-4-methyl- Preferred imidazole and phosphorus compounds include triphenylphosphine, and preferred tertiary amines include N,N-dimethyl-4-aminopyridine (DMAP) and 1,8-diazabicyclo-[5.4.0]-undecene (DBU).

<Other formulations>
The glass fiber-containing resin composition of the present invention may contain other ingredients. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, Examples include antioxidants, flame retardants, plasticizers, and the like.

<Cured product>
The cured product of the present invention can be obtained by curing the glass fiber-containing resin composition. The cured product has low linear expansion, high glass transition temperature, and excellent thermal decomposition resistance, so it can be suitably used as a heat-resistant member. Also, since it has excellent adhesion to glass fibers, it has high mechanical strength. It can also be suitably used in molding materials reinforced with glass fiber. The method for molding the cured product is not particularly limited, and the composition may be molded alone, or a laminate may be formed by having (laminating) a layer made of the cured product together with the base material.

When curing the glass fiber-containing resin composition of the present invention, thermal curing may be performed. When thermally curing, a known and commonly used curing catalyst may be used, but the glass fiber-containing resin composition can be cured without using a curing catalyst due to the reaction between the maleimide group and the allyl group.
When thermal curing is performed, it may be cured by one heating process or may be cured through a multi-step heating process.

When using a curing catalyst, for example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; Titanate esters such as isopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) , 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 2-ethyl-4-methyl-imidazole, 1-methylimidazole, N , N-dimethyl-4-aminopyridine (DMAP) and other compounds containing various basic nitrogen atoms; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc. and quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate. Tin carboxylates, such as; benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate Organic peroxides such as, for example, can be used. The catalysts may be used alone or in combination of two or more.

Further, since the (meth)allyl group-containing maleimide compound has a carbon-carbon double bond, it can also be cured with active energy rays. When performing active energy ray curing, a photopolymerization initiator may be added to the glass fiber-containing resin composition. Any known photopolymerization initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. The acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone and the like. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like. The photopolymerization initiators may be used alone or in combination of two or more.

When curing is carried out using both thermal curing and active energy ray curing, heating and active energy ray irradiation may be performed simultaneously or separately. For example, thermal curing may be performed after active energy ray irradiation, or active energy ray curing may be performed after thermal curing. Moreover, each curing method may be combined two or more times, and the curing method may be selected as appropriate depending on the application.

<Compound>
The present invention relates to a compound containing the glass fiber-containing resin composition. The method for obtaining the compound includes uniformly mixing the glass fiber-containing resin composition, a curing accelerator, and other fillers using an extruder, kneader, roll, etc. as necessary. An example of this method is to sufficiently melt and mix the mixture until it becomes . In this case, as other fillers, organic colorants such as carbon black, inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride, etc. with high thermal conductivity are used. The filling rate of the inorganic filler is preferably 30 to 95% by mass per 100 parts by mass of components other than glass fibers in the glass fiber-containing resin composition. In order to improve cracking properties and reduce the coefficient of linear expansion, the content is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

<Heat-resistant parts>
The present invention relates to a composition for heat-resistant materials containing the glass fiber-containing resin composition. The present invention also relates to a heat-resistant member containing a cured product obtained by curing the glass fiber-containing resin composition. The glass fiber-containing resin composition of the present invention can be suitably used for heat-resistant members because its cured product has low linear expansion and excellent thermal decomposition resistance. As a molding method for obtaining a heat-resistant member from the glass fiber-containing resin composition of the present invention, the above compound is molded using a casting, transfer molding machine, injection molding machine, etc., and then at 50 to 250°C for 2 to 10 hours. Examples include a method of heating. The heat-resistant components thus obtained can be suitably used for various purposes, such as industrial mechanical parts, general mechanical parts, automobile/railway/vehicle parts, space/aviation related parts, electronic/electrical parts, building materials, etc. Examples include, but are not limited to, containers/packaging members, daily necessities, sports/leisure goods, wind power generation casing members, etc.

Next, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited to these. Further, in the following, "parts" and "%" are based on mass unless otherwise specified. Note that ¹ H-NMR, ¹³ C-NMR, and FD-MS spectra were measured under the following conditions.

¹ H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE
Magnetic field strength: 600MHz
Total number of times: 32 times Solvent: DMSO-d6
Sample concentration: 30% by mass

^13C -NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE
Resonance frequency: 100MHz
Accumulation count: 4000 times Solvent: Chloroform-d
Sample concentration: 12% by mass
Relaxation reagent: Chromium (III) acetylacetonate

FD-MS: “JMS-T100GC AccuTOF” manufactured by JEOL Ltd.
Measurement range: m/z=50.00-2000.00
Rate of change: 25.6mA/min
Final current value: 40mA

Production Example 1 Fiber sizing agent (A): Use of polyester resin containing polymerizable double bonds Neopentyl glycol 104 parts by mass (1 mol part), butyrolactone 172 parts by mass (2 mol parts), and potassium oxalate titanate 2 Part by mass was reacted in a glass reaction vessel at 230° C. for 15 hours while reducing the pressure to 0.001 MPa and distilling off water. Further, 88 parts by mass (0.9 parts by mole) of maleic anhydride was added to the reaction mixture, and the mixture was reacted at 150° C. and normal pressure for 2 hours to obtain a polyester resin. Next, 1,100 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes. This aqueous dispersion was concentrated by vacuum distillation to obtain a fiber sizing agent (A) with a solid content of 30%. The double bond concentration in the obtained focusing agent was calculated from the integral value of ¹³ C-NMR and was 5 mol%. Note that the double bond concentration was calculated from the ratio of the integral value of all the ¹³ C-NMR signals to the half of the integral value of the signal around 98 to 100 ppm.

Production Example 2 Fiber sizing agent (B): Use of polyurethane resin containing polymerizable double bonds Polycaprolactone ester polyol (trade name: Plaxel 220 [PCL220], manufactured by Daicel Chemical Co., Ltd., OH value 56 mgKOH/g, Mw: 2000) and 1710 parts by mass of polybutadiene with hydroxyl groups at both ends (NISSO-PB[G-2000] manufactured by Nippon Soda Co., Ltd., number average molecular weight: 1900) were added and dissolved in 500 parts by mass of methyl ethyl ketone, and then dissolved in xylene. 188 parts by mass of diisocyanate was added and reacted at 80°C for 2 hours to obtain a polyurethane resin solution.Next, 1200 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes.This aqueous dispersion was It was concentrated by vacuum distillation to obtain a fiber sizing agent (B) with a solid content of 30%.The double bond concentration in the obtained sizing agent was calculated from the integral value of ^13C -NMR and was 21 mol%. Note that the double bond concentration was calculated from the ratio of the integral value of all ¹³ C-NMR signals to the half of the integral value of the signal around 98 to 100 ppm.

Production Example 3 Fiber sizing agent (C): Use of polyester resin that does not contain polymerizable double bonds Neopentyl glycol 104 parts by mass (1 mol part), butyrolactone 172 parts by mass (2 mol parts), and potassium oxalate titanate 2 Part by mass was reacted in a glass reaction vessel at 230°C for 15 hours while reducing the pressure to 0.001 MPa and distilling off water to obtain a polyester resin. Next, 1,100 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes. This aqueous dispersion was concentrated by vacuum distillation to obtain a fiber sizing agent (C) with a solid content of 30%.

Production Example 4 Fiber sizing agent (D): Use of polyurethane resin containing only 1 mole of polymerizable double bonds Polycaprolactone ester polyol (trade name: Plaxel 220 [PCL220], manufactured by Daicel Chemical Co., Ltd., OH value 56 mgKOH/g , Mw: approx. 2000), 5.7 parts by mass of polybutadiene with hydroxyl groups at both ends (NISSO-PB [G-2000] manufactured by Nippon Soda Co., Ltd., number average molecular weight: 1900) and 100 parts by mass of methyl ethyl ketone were added and dissolved. Then, 18 parts by mass of xylene diisocyanate was added and reacted at 80° C. for 2 hours to obtain a polyurethane resin solution. Next, 1200 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes. This aqueous dispersion was concentrated by vacuum distillation to obtain a fiber sizing agent (D) with a solid content of 30%.The double bond concentration in the obtained sizing agent was calculated from the integral value of ¹³ C-NMR. The double bond concentration was calculated from the ratio of the integral value of all the ¹³ C-NMR signals to the half of the integral value of the signal around 98 to 100 ppm.

Production Example 5 Fiber sizing agent (E): Polyvinyl acetate resin containing no polymerizable double bonds In a 200-liter autoclave equipped with a stirrer, 185 parts by mass of ion-exchanged water, 85 parts by mass of ethyl alcohol, and 100 parts by mass of vinyl acetate monomer. 0.3 parts by mass of bis(4-tert-butylcyclohexyl) peroxydicarbonate [manufactured by Kayaku Akzo Co., Ltd., Percadox 16] as a polymerization catalyst, 0.025 parts by mass of partially saponified polyvinyl alcohol as a suspension stabilizer. Parts by mass were charged, and polymerization was carried out at a polymerization temperature of 62° C. for 7 hours. Next, while stirring the slurry, unreacted vinyl acetate monomer and ethyl alcohol were removed at a temperature of 65°C and a reduced pressure of -580 mmHg to obtain an aqueous polyvinyl acetate resin solution. Next, 370 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes. This aqueous dispersion was concentrated by vacuum distillation to obtain a fiber sizing agent (E) with a solid content of 30%.

[Synthesis Example 1] Synthesis of maleimide composition (A) Proceedings of the National Academy of Sciences, India, Section A: Physical Sciences, 71(1), 5-12; 2001, The reactants were prepared according to methods described in the literature. (h-1) was synthesized.

60.00 g (0.232 mol) of reactant (h-1), 800 mL of acetic acid, and 800 mL of hydrobromic acid (47%) were placed in a 3 L flask equipped with a thermometer, cooling tube, and stirrer, and heated while stirring to bring the mixture to reflux. And so. After reacting under reflux for 12 hours, the mixture was air-cooled to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with 600 mL of ethyl acetate. The mixture was washed three times with 200 mL of ion-exchanged water, dried over sodium sulfate, and concentrated under reduced pressure to obtain 43.01 g (yield: 80.5%) of reaction product (h-2).

133.40 g (0.58 mol) of reactant (h-2), 1 L of DMF (N,N-dimethylformamide), and 0.45 L of ion-exchanged water were placed in a 3 L flask equipped with a thermometer, cooling tube, and stirrer, and the mixture was heated at room temperature. Stirred. After heating the reaction solution to 60° C., 148.22 g (1.45 mol) of acetic anhydride was slowly added dropwise. After the dropwise addition was completed, the mixture was reacted at 60° C. for 2 hours, and then air-cooled to room temperature. The precipitate was filtered, washed with 2 L of ion-exchanged water, and then vacuum-dried at 80° C. for 10 hours to obtain 162.09 g (yield: 89.0%) of solid reaction product (a-1).

137.53 g (0.438 mol) of reactant (a-1) and 2.2 L of acetone were charged into a 3 L flask equipped with a thermometer, a cooling tube, and a stirrer, and the mixture was stirred. Next, 133.79 g (0.968 mol) of potassium carbonate was added, and the reaction solution was heated to a reflux state. After refluxing for 1 hour, 116.60 g (0.964 mol) of allyl bromide was added dropwise over 1 hour. After the dropwise addition was completed, the reaction mixture was allowed to react under reflux for 12 hours, and then air-cooled to room temperature. After filtration, the reaction solution was concentrated under reduced pressure and further vacuum dried at 80° C. for 10 hours to obtain 165.67 g (yield 96.0%) of reaction product (a-2).

A 1 L flask equipped with a thermometer, a cooling tube, and a stirrer was charged with 158.39 g (0.402 mol) of the reaction product (a-2) and 330 mL of ethanol and stirred. 108.97 g of concentrated hydrochloric acid was added and heated to 60°C. After reacting at 60°C for 30 hours, it was air cooled to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with 400 mL of ethyl acetate. Washed twice with 200 mL of ion-exchanged water, added sodium sulfate, dried, and concentrated under reduced pressure. The resulting reaction product was vacuum-dried at 80°C for 10 hours to obtain 117.14 g of liquid reactant (h-3). Yield: 94.0%).

132.48 g (1.351 mol) of maleic anhydride and 1.53 L of toluene were charged into a 3 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, and the mixture was stirred at room temperature. The flask was transferred to an ice bath, and a mixed solution of 99.82 g (0.322 mol) of the reaction product (h-3), 63.76 g (0.584 mol) of 4-aminophenol, and 280 mL of DMF was added dropwise. After the dropwise addition was completed, the reaction was continued for an additional 2 hours at room temperature. 15.27 g of p-toluenesulfonic acid monohydrate was added, the reaction solution was heated, and the water and toluene that azeotroped under reflux were cooled and separated. Only the toluene was returned to the system to complete the dehydration reaction. Time went. After air cooling to room temperature, the mixture was concentrated under reduced pressure to obtain 553.22 g of a brown solution. Dissolved in 1.4 L of ethyl acetate, washed 4 times with 400 mL of ion-exchanged water and 5 times with 400 mL of 2% sodium bicarbonate aqueous solution, added with sodium sulfate, dried, and concentrated under reduced pressure. The resulting reaction product was heated at 80°C for 11 hours. Vacuum drying was performed to obtain 183.04 g of a maleimide composition (A) containing an allyl group-containing maleimide compound and a hydroxyl group-containing maleimide compound.

The mass spectrum of the obtained maleimide composition (A) showed peaks at M ⁺ =470 and 189, confirming that the desired maleimidization was progressing. Furthermore, it was confirmed by ¹ H-NMR that the ratio of maleimide components was allyl group-containing maleimide/hydroxyl group-containing maleimide = 72:28 (weight ratio). In calculating the ratio, a signal derived from the allyl group of the allyl group-containing maleimide and a signal derived from the aromatic ring of the hydroxyl group-containing maleimide in ¹ H-NMR were used.

(Example 1)
[Preparation of glass fiber coated with resin composition (coated glass fiber)]
Using the fiber sizing agent (A) obtained in Production Example 1, coated glass fibers having a diameter of 6.5 μm and a length of 1.5 mm were produced by the chopped strand method. At this time, the weight of the fiber sizing agent (A) attached (coated) was 1% by mass as a solid content based on the total mass of the coated glass fibers.

[Preparation of glass fiber-containing resin composition (compound)]
146 parts by mass of the obtained coated glass fiber, 160 parts by mass of the maleimide composition (A) obtained in Synthesis Example 1, and 55 parts by mass of EPICLON HP-4700 (manufactured by DIC Corporation, epoxy resin). , 2 parts by mass of rice wax (manufactured by Cerarica NODA Co., Ltd.) as a mold release agent, 2 parts by mass of carbon black (manufactured by Mitsubishi Chemical Corporation) as a coloring agent, and imidazole (manufactured by Shikoku Kasei Co., Ltd.) as a curing catalyst. 1 part by mass of 2E4MZ (manufactured by Kogyo Co., Ltd.) was heated to 100 to 110°C for 4 minutes, and then heated to 140°C for 10 minutes using a φ8" x L20" continuous roll machine (manufactured by Kansai Roll Co., Ltd.). The mixture was heated to 140° C. and kneaded until uniform, thereby preparing a glass fiber-containing resin composition.

[Manufacture of molded object]
The obtained glass fiber-containing resin composition was press-molded at 180°C for 3 minutes at a pressure of 20 MPa using a compression molding machine manufactured by Shindo Metal Industry Co., Ltd., and cured to a size conforming to JIS K6911. A molded object was manufactured. The obtained molded body was post-heated at 200° C. for 2 hours.

(Example 2)
In Example 2, a glass fiber-containing resin composition and a molded article were produced and evaluated in the same manner as in Example 1, except that the glass fibers were changed to a diameter of 11 μm and a length of 3 mm.

(Example 3 and Comparative Examples 1 to 3)
For Example 3 and Comparative Examples 1 to 3, glass fiber-containing resin compositions and molded bodies were manufactured and evaluated under the same conditions as Example 1 except for the changes shown in Table 1. did.

(Comparative example 4)
Regarding Comparative Example 4, the changes in Example 1 were made as shown in Table 1, using a phenol resin (manufactured by DIC Corporation, trade name: KI-9544) instead of the maleimide resin composition (A). A glass fiber-containing resin composition and a molded article were manufactured and evaluated under the same conditions except for the following.

(Comparative example 5)
Comparative Example 5 was the same as Example 1 except that 4,4-diphenylmethane bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-1000) was used instead of the maleimide resin composition (A). produced a glass fiber-containing resin composition under the same conditions and evaluated only the fiber dispersibility.

<Evaluation>
[Fiber dispersibility evaluation (wetting and adhesion to glass fiber)]
In the preparation of a glass fiber-containing resin composition, the state of fluff of the glass fibers in the compound when heated at 100 to 110 °C for 4 minutes, then raised to 140 °C for 10 minutes, and continued kneading at 140 °C for 4 minutes. was visually judged according to the following criteria.
○: No fuzz was observed, or some fuzz was observed, but the level was not a problem for practical use.
Δ: Fuzzing was observed, and some fibers were also exposed. There are practical problems.
×: Very much fluff and fibers were exposed, and a dry feeling was observed as a whole. There are practical problems.

[Evaluation of molded object]
The obtained molded body was evaluated for mechanical strength in terms of tensile strength test, elastic modulus, and elongation at break in accordance with JIS K6911.
The tensile strength of the obtained molded product, which is the cured product, is preferably 60 MPa or more, more preferably 60 to 80 MPa, both at room temperature (23 ° C.) and 150 ° C. (high temperature). More preferably, it is 70 to 80 MPa. If it is within the above range, it will be practically excellent.
The elastic modulus is preferably 1450 MPa or more, more preferably 1550 to 1800 MPa, and still more preferably 1650 to 1800 MPa, both at room temperature (23° C.) and 150° C. (high temperature). If it is within the above range, it will be practically excellent.
The elongation at break is preferably 4% or more, more preferably 4 to 6%, even more preferably 4.5 to 6%, both at room temperature (23°C) and 150°C (high temperature). It is 6%. When it is within the above range, a high elastic modulus and a high elongation rate, which are contradictory, can be achieved at the same time, resulting in an excellent product for practical use.

From the results in Table 2 above, in Examples 1 to 3, by using a glass fiber-containing resin composition containing glass fibers coated with a specific resin composition together with two types of maleimide compounds having a specific structure, The obtained molded product, which is a cured product, is superior in tensile strength, elastic modulus, and elongation at break, which are indicators of mechanical strength, compared to comparative examples that do not use a maleimide compound with a specific structure or glass fiber. It could be confirmed. In addition, in Comparative Example 5, a commonly used highly heat-resistant BMI was used and a maleimide compound with a specific structure was not used, so it was difficult to melt and knead the glass fibers (100 to 140°C). It was also confirmed that the wettability and adhesion to glass fibers were poor, and that it was not possible to reduce the viscosity.

The glass fiber-containing resin composition of the present invention provides a cured product with excellent heat resistance and mechanical strength, so it can be suitably used for compounds, heat-resistant members, etc. using the glass fiber-containing resin composition.

Claims (7)

A (meth)allyl group-containing maleimide compound represented by the following formula (1),
A hydroxyl group-containing maleimide compound represented by the following formula (4), and
Contains a glass fiber coated with a resin composition containing at least one of a polyester resin and a polyurethane resin, containing a polymerizable double bond concentration of 3 mol% or more and 25 mol% or less ,
The glass fiber is characterized in that the polymerizable double bond concentration is calculated from the ratio of the integral value of all signals of ¹³ C-NMR to the integral value of a signal around 98 to 100 ppm. Containing resin composition.
(In the above formula (1), n ₁ and m ₁ are each independently an integer of 1 to 5, and Aly is a group having a (meth)allyl group represented by the following formula (2), MI is a group having a maleimide group represented by the following formula (3), and A ₁ is any of the structures represented by the following formula (5) .)
(In the above formula (2), Z ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may have a direct bond or a substituent, and R ¹ represents a hydrogen atom or a methyl group.)
(In the above formula (3), Z ₂ is a hydrocarbon group having 1 or 2 carbon atoms which may have a direct bond or a substituent, and R ² and R ³ are each independently a hydrogen atom or a methyl (Represents a group.)
(In the above formula (4), n ₂ and m ₂ are each independently an integer of 1 to 5, MI is a group having a maleimide group represented by the above formula (3), and A ₂ is It is a benzene ring structure .)
The glass fiber-containing resin composition according to claim 1 , wherein in the formula (4) , both n2 _{and m2} are 1. The glass fiber-containing resin composition according to claim 1 or 2, further comprising an epoxy compound. A compound comprising the glass fiber-containing resin composition according to any one of claims 1 to 3 . A cured product obtained by curing the glass fiber-containing resin composition according to any one of claims 1 to 3 . A composition for heat-resistant materials, comprising the glass fiber-containing resin composition according to any one of claims 1 to 3 . A heat-resistant member comprising the cured product according to claim 5 .