JP2023003713A - Curable resin composition and method for producing curable resin composition, and viscosity modifier, cured product, and electric/electronic component - Google Patents

Abstract

To provide a curable resin composition that gives a cured product having high handleability at low viscosity, high bending strength, fracture toughness, and adhesive strength, and high long-term reliability.SOLUTION: A curable resin composition contains a propenyl group-containing compound represented by the following formula (1), and an epoxy compound having a specific structure. (X is a direct bond, -SO2-, -O-, -CO-, -C(CF3)2-, -S- or a C1-20 aliphatic hydrocarbon group. R1 and R2 each denote a hydrogen atom, a C1-10 hydrocarbon group or a halogen atom).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a curable resin composition, a method for producing the curable resin composition, a viscosity modifier, a cured product, and an electric/electronic component. More particularly, the present invention relates to a curable resin composition containing a propenyl group-containing compound and an epoxy compound having a specific structure, a method for producing the same, a viscosity modifier, a cured product, and an electrical/electronic component.

A thermosetting resin composition is used in various fields as a thermosetting molding material or the like by utilizing its curability. Examples thereof include adhesives and sealing materials in electrical and electronic parts.

As a thermosetting resin composition, a resin composition in which allylphenol, alkenylphenol, alkenylphenol ether, or the like is mixed with maleimide resin or epoxy resin has been proposed.

For example, Patent Documents 1 and 2 disclose compositions comprising mixtures of bismaleimide and amines, alkenylphenols, alkenylphenol ethers, etc., and the alkenylphenols are produced by rearrangement of allyl ethers of phenols. is disclosed.

Further, in Patent Document 3, a specific propenyl group-containing resin having a benzene ring or a naphthalene ring having a propenyl group and 1 A resin composition containing a maleimide compound having two or more maleimide groups in the molecule is disclosed.

JP-A-62-181335 JP-A-4-227931 JP 2019-019149 A

In the past, most semiconductors were used with relatively small currents and power, such as LSIs, but in recent years, the development of power semiconductors, which use semiconductors to control motors, lighting, etc. and to convert power, has been rapid. progressing to Along with this, semiconductors and semiconductor encapsulation materials that can be used with higher power and current than before are desired, and semiconductor encapsulation materials have lower viscosity, higher mechanical strength and long-term reliability than before. It has been demanded.

The cured product obtained by curing the resin composition containing the propenyl group-containing resin and the maleimide compound described in Patent Document 3 has low viscosity, high mechanical strength and high mechanical strength as a semiconductor sealing material used for the above-mentioned applications. The long-term reliability was not satisfactory.

Moreover, in industrially producing a curable resin composition or a cured product using a propenyl group-containing compound, there has been a problem that it is difficult to control viscosity, gel time, etc., and industrial handleability is low.
Further, the cured product obtained by curing the curable resin composition using the propenyl group-containing compound has the problem of low bending strength, fracture toughness, and adhesion strength of the cured product to metals.

Therefore, the present invention provides a curable resin that has low viscosity, high industrial handling properties, high bending strength and fracture toughness when cured, high adhesive strength to metals, and excellent long-term reliability. An object of the present invention is to provide a composition, a viscosity modifier therefor, a cured product thereof, and electric/electronic parts.

As a result of intensive studies to solve the above problems, the present inventor found that a curable resin composition obtained by mixing an epoxy compound having a specific structure and a propenyl group-containing compound can solve the above problems, and completed the present invention. came to.

That is, the gist of the present invention resides in the following [1] to [6].

[1] A curable resin composition containing a propenyl group-containing compound represented by the following formula (1) and an epoxy compound represented by the following formula (2).

(In formula (1) above, X is a divalent linking group, which is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S—, or carbon number an aliphatic hydrocarbon group of 1 to 20. R ¹ and R ² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.)

[2] Maleimide resin, phenolic resin, benzoxazine resin, cyanate ester resin, Curing according to [1], containing 0.01 to 1000 parts by mass of at least one selected from the group consisting of active ester resins, resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins and carbodiimide resins. elastic resin composition.

[3] A cured product obtained by curing the curable resin composition according to [1] or [2].

[4] An electric/electronic component containing the cured product of [3].

[5] An epoxy compound represented by the following formula (2), a maleimide resin, a phenolic resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, and an acid anhydride A viscosity modifier containing at least one selected from the group consisting of a resin and a carbodiimide resin.

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.)

[6] An epoxy compound represented by the following formula (2), a maleimide resin, a phenolic resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, and an acid anhydride A curable resin obtained by premixing at least one selected from the group consisting of a resin and a carbodiimide resin, and then mixing the mixture with a propenyl group-containing compound represented by the following formula (1) to obtain a curable resin composition. A method of making the composition.

(In formula (1) above, X is a divalent linking group, which is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S—, or carbon number an aliphatic hydrocarbon group of 1 to 20. R ¹ and R ² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.)

The curable resin composition of the present invention containing a propenyl group-containing compound represented by formula (1) and an epoxy compound represented by formula (2), and further the curable resin composition of the present invention containing a maleimide resin, etc. It is possible to provide a highly reliable cured product having excellent mechanical strength such as bending strength and fracture toughness and adhesion strength to metal, and a cured product that can provide electric and electronic parts.
In addition, the curable resin composition of the present invention has a low viscosity and a moderately long gel time, and is therefore excellent in handleability on an industrial scale.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist of the present invention. Absent. In addition, when the expression "~" is used in this specification, it is used as an expression including numerical values or physical property values before and after it.

The curable resin composition of the present invention is characterized by containing a propenyl group-containing compound represented by formula (1). The structure represented by formula (1) does not contain a repeating structure, but is a monomolecular structure. , "propenylphenol" or "propenylphenol resin". It is also sometimes sold as "phenolic resin". In the industry, a curable resin composition containing a propenyl group-containing compound represented by formula (1) is called a "phenolic compound (uncured one)" or a "phenolic resin". sometimes.

The propenyl group-containing compound contained in the curable resin composition of the present invention is a compound represented by formula (1) (hereinafter sometimes referred to as "propenyl group-containing compound (1)") and Since it contains other optional components (e.g., the propenyl group-containing compound represented by the formula (1A) below and trace impurities), in the technical field of the compound, the "propenyl group-containing compound" consists of a single component. Other than that, it may be acquired as a "composition" consisting of multiple components. Therefore, the propenyl group-containing compound represented by formula (1) is referred to in the art as a "propernyl group-containing composition" (sometimes referred to as a "propenyl group-containing resin"), or as a "propenyl group-containing containing composition” (sometimes referred to as “propenyl group-containing resin”).
In the following, the propenyl group-containing compound itself represented by formula (1) is referred to as "propenyl group-containing compound (1)", and the propenyl group-containing compound (1) and propenyl represented by formula (1A) described later A propenyl group-containing compound as a composition containing a group-containing compound (hereinafter sometimes referred to as "propenyl group-containing compound (1A)") may be referred to as "propenyl group-containing compound (I)". .

Further, the curable resin composition of the present invention is characterized by containing an epoxy compound represented by formula (2) (hereinafter sometimes referred to as "epoxy compound (2)"). The structure represented by formula (2) includes not only one containing a repeating structure but also a monomolecular structure. ” is sometimes expressed. It is also sometimes sold as "epoxy resin". In the industry, a curable resin composition containing an epoxy compound represented by formula (2) is sometimes called an "epoxy resin".

[Curable resin composition]
The curable resin composition of the present invention is characterized by containing a propenyl group-containing compound represented by the following formula (1) and an epoxy compound represented by the following formula (2).

(In formula (1) above, X is a divalent linking group, which is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S—, or carbon number an aliphatic hydrocarbon group of 1 to 20. R ¹ and R ² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.)

As described above, propenyl group-containing compound (1) is usually contained in the curable resin composition of the present invention as propenyl group-containing compound (I).

[Propenyl group-containing compound (I)]
<Propenyl group-containing compound (1)>
In the formula (1) representing the propenyl group-containing compound (1) according to the present invention, the aliphatic hydrocarbon group having 1 to 20 carbon atoms for X is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, An optionally branched alkylene group having 1 to 10 carbon atoms is particularly preferred. X is preferably a direct bond or a C 1-10 aliphatic hydrocarbon group, more preferably a direct bond, a methylene group or an isopropylidene group, and most preferably a direct bond.

Halogen atoms for R ¹ and R ² include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms for R ¹ and R ² include alkyl groups having 1 to 10 carbon atoms. Preferably, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and most preferably both R ¹ and R ² are hydrogen atoms.

The propenyl group-containing compound (1) represented by formula (1) is a cis-trans isomer of the double bond of the propenyl group (1-propenyl group) attached to each of the two benzene rings. and includes a “trans form” in which both propenyl groups in formula (1) are trans-type, and a “cis-form” in which both are cis-type.

The ratio of the trans isomer in the propenyl group-containing compound (1) is not particularly limited, but is preferably 20 to 95%, more preferably 30 to 85%, still more preferably 45 to 75%. The larger the ratio of the trans isomer, the higher the crystallinity, and the better the handleability of the powder tends to be, and the smaller the ratio, the better the solubility in a solvent.

The proportion of the cis isomer in the propenyl group-containing compound (1) is not particularly limited, but is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The smaller the proportion of the cis form, the higher the crystallinity and the better the handleability of the powder tends to be. Although the lower limit of the ratio of the cis isomer is not particularly limited, it is preferably 1% or more from the viewpoint of melting property during heating.

The propenyl group-containing compound (1) also includes other propenyl group-containing compounds (1) that are neither trans nor cis. One of the two propenyl groups in formula (1) is trans-type and the other is cis-type, and is usually contained in the propenyl group-containing compound (1) at about 5 to 50%.

The ratio of the trans- and cis-isomers of the propenyl group-containing compound (1) can be controlled by, for example, changing the type of solvent used in the propenylation reaction during the production of the propenyl group-containing compound (1). can.

As described above, propenyl group-containing compound (1) is usually included in the curable resin composition of the present invention as propenyl group-containing compound (I).

Propenyl group-containing compound (I) is not particularly limited, but preferably contains 80.0 to 99.9% by mass of propenyl group-containing compound (1). When the content of the propenyl group-containing compound (1) in the propenyl group-containing compound (I) is less than 80.0% by mass, high heat resistance, low viscosity and long-term reliability due to the inclusion of the propenyl group-containing compound (1) A sufficient effect may not be obtained. Propenyl group-containing compound (I) consisting of 100% by mass of propenyl group-containing compound (1) is practically difficult to produce. The amount is 99.9% by mass or less. While enhancing the effect of the propenyl group-containing compound (1), from the viewpoint of solubility in solvents, the content of the propenyl group-containing compound (1) in the propenyl group-containing compound (I) is preferably 85.0. ~99.8% by mass, more preferably 90.0 to 99.5% by mass.

In the propenylation reaction for producing the propenyl group-containing compound (1), the propenyl group-containing compound (1A) described below may remain. The content of the later-described propenyl group-containing compound (1A) in the propenyl group-containing compound (I) is not particularly limited, but can be controlled by, for example, changing the amount of solvent used in the propenylation reaction.
In order to decrease the amount of the propenyl group-containing compound (1) and increase the amount of the propenyl group-containing compound (1A), for example, the amount of the solvent can be increased. In order to reduce the group-containing compound (1A), it can be controlled by, for example, reducing the amount of solvent.

In the case where the propenyl group-containing compound (I) according to the present invention consists of the propenyl group-containing compound (1) and the propenyl group-containing compound (1A) described later, a trace amount of impurities may be added during the production of the propenyl group-containing compound (1). may be included. Unavoidable impurities during the production of the propenyl group-containing compound (1) can be reduced by purifying the obtained propenyl group-containing compound by washing with water, chromatographic separation, crystallization, and the like.

<Propenyl group-containing compound (1A)>
The propenyl group-containing compound (I) according to the present invention is a compound having a 2-propenyl group (allyl group) represented by the following formula (1A) (hereinafter referred to as "propenyl group-containing compound (1A)" ), in which case the content of the propenyl group-containing compound (1A) is preferably 0.1 to 20.0% by mass.

(In formula (1A) above, X, R ¹ and R ² have the same definitions as in formula (1) above.)

The propenyl group-containing compound (I) according to the present invention tends to have a lower melt viscosity as the amount of the propenyl group-containing compound (1A) increases. Curing time tends to be longer. From such a viewpoint, the content of the propenyl group-containing compound (1A) in the propenyl group-containing compound (I) according to the present invention is preferably 0.2 to 10.0% by mass, more preferably 0.3. ~5.0% by mass.

<Method for Producing Propenyl Group-Containing Compound (1)>
The method for producing the propenyl group-containing compound (1) is not particularly limited. ) to obtain an allyloxy group-containing compound represented by the following formula (4) (hereinafter sometimes abbreviated as “allyloxy group-containing compound (4)”), and then an allyloxy group-containing compound The allyl group of (4) is transferred to obtain the aforementioned propenyl group-containing compound (1A), and the allyl group of this propenyl group-containing compound (1A) is changed to a 1-propenyl group to obtain the propenyl group-containing compound (1). method.

(In formulas (3) and (4) above, X, R ¹ and R ² have the same meanings as in formula (1) above.)

As a method for allylating the dihydric phenol compound (3), for example, the dihydric phenol compound (3) is reacted with an allyl halide, and at least part of the hydroxyl groups are allyl-etherified to form —O—CH ₂ —CH. = _CH2 .

In this reaction, the allyl halide is used in an amount of 2.0 to 8.0 times the moles of the dihydric phenol compound (3), particularly 3.0 to 6.0 times the moles of the dihydric phenol compound (3). , is preferable from the viewpoint of suppressing the production cost.

The allyl etherification reaction between the dihydric phenol compound (3) and allyl halide is preferably carried out in the presence of a catalyst.

Examples of catalysts for the allyl etherification reaction include alkali metals such as sodium hydroxide, potassium hydroxide and potassium carbonate; amines such as diazabicyclononene, diazabicycloundecene and triethylamine; sodium tert-butoxide; tert-butoxide, lithium diisopropylamide, silicon-basic amines, lithium tetramethylpiperidine and the like. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferable because they are relatively inexpensive and less likely to cause side reactions. A catalyst may be used individually by 1 type, and may use 2 or more types together.

The amount of the catalyst used in the allyl etherification reaction is preferably 0.7 to 2.0 times the molar amount of the allyl halide used, and more preferably 0.8 to 1.5 times the molar amount. If the amount of catalyst used is too small, the reaction rate will be slow.

Moreover, the allyl etherification reaction is preferably carried out in the presence of a solvent, and examples of the solvent for the allyl etherification reaction include polar solvents used in the propenylation reaction described later.

The reaction temperature for the allyl etherification reaction is not particularly limited as long as it is a temperature at which the hydroxyl group of the dihydric phenol compound (3) reacts with the allyl halide.

After the allyl etherification reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.).

The allyl group transfer of the allyloxy group-containing compound (4) obtained by allylation of the dihydric phenol compound (3) is, for example, a Claisen rearrangement reaction by heating the allyloxy group-containing compound (4) after the allylation reaction. can be implemented in Due to the Claisen rearrangement reaction, the allyl group of the allyloxy group (—O—CH ₂ —CH═CH ₂ ) bonded to the benzene ring of the allyloxy group-containing compound (4) is rearranged to the ortho position where the allyloxy group was present.

Claisen rearrangement reaction may be carried out according to a conventional method, for example, allyloxy group-containing compound (4) in the presence of a high boiling point solvent such as carbitol, paraffin oil, N,N'-dimethylaniline, N,N'-diethylaniline or Heat in the absence of solvent. 10 to 200 parts by mass of the solvent is used as necessary with respect to 100 parts by mass of the allyloxy group-containing compound (4). After completion of the reaction, if necessary, the solvent used can be removed to obtain the propenyl group-containing compound (1A). After the reaction, the propenyl group-containing compound (1A) can be recovered by dropping the reaction solution into an aqueous sodium hydroxide solution, dropping the separated aqueous layer into an acid solution, and stirring.

The heating temperature for this Claisen rearrangement reaction is preferably 150 to 220° C., more preferably 170 to 200° C., and the rearrangement reaction in the presence of an inert gas such as nitrogen is even more preferable. If the heating temperature is equal to or higher than the above lower limit, rearrangement reaction of allyl groups easily occurs. When the heating temperature is equal to or lower than the above upper limit, polymerization of allyl groups is less likely to occur.

After the reaction, if necessary, the reaction product may be subjected to a treatment such as washing with water.

The time for dropping into the aqueous sodium hydroxide solution after the reaction is preferably 10 to 30 minutes. If the dropping time is at least the above lower limit, heat generation due to mixing can be suppressed and production can be carried out safely. If the dropping time is equal to or less than the above upper limit, productivity will improve. The stirring time after dropping into the acid solution is preferably 15 to 60 minutes. If the stirring time is at least the above lower limit, the neutralization reaction proceeds and the yield in the subsequent separation step is improved. If the stirring time is equal to or less than the above upper limit, productivity will improve.

A method of converting the allyl group of the propenyl group-containing compound (1A) into a 1-propenyl group includes a method of dissolving the propenyl group-containing compound (1A) in a solvent and heating under the presence of a propenylation reaction catalyst.

The solvent used in the propenylation reaction may be any solvent as long as it dissolves the propenyl group-containing compound (1A), and typically includes polar solvents.
Polar solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, Ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran. As the solvent, one type may be used alone, or two or more types may be used in combination.

The solvent is preferably used in an amount of 20 to 900 parts by mass, particularly 50 to 600 parts by mass, per 100 parts by mass of the propenyl group-containing compound (1A).

Catalysts for the propenylation reaction include, for example, alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononene, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide, Lithium diisopropylamide, silicon-basic amines, lithium tetramethylpiperidine and the like. Among them, potassium hydroxide and sodium hydroxide are preferable because they are relatively inexpensive and less likely to cause side reactions. A catalyst may be used individually by 1 type, and may use 2 or more types together.

The amount of the propenylation reaction catalyst used is preferably 0.4 to 6.0-fold mol, more preferably 1.0 to 4.0-fold mol, relative to the total molar amount of hydroxyl groups in the propenyl group-containing compound (1A). preferable. If the amount of the catalyst used is too small, the propenylation reaction will be difficult to proceed.

The reaction temperature for the propenylation reaction is preferably 40 to 140°C, more preferably 70 to 120°C. When the reaction temperature is at least the above lower limit, the propenylation reaction proceeds easily. When the reaction temperature is equal to or lower than the above upper limit, polymerization of propenyl groups is less likely to occur.

After the propenylation reaction, if necessary, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.).

In the production of the propenyl group-containing compound (1) as described above, the propenyl group-containing compound (1A) remains to obtain the propenyl group-containing compound (I) according to the present invention, but the curable resin composition of the present invention When it is desired to contain the propenyl group-containing compound (I) according to the present invention in a product, in the present invention, the propenyl group-containing compound (1) after the propenylation reaction and the propenyl group-containing compound (1A) are blended to obtain the present It may be used as the propenyl group-containing compound (I) according to the invention.

[Epoxy compound (2)]
In the formula (2) representing the epoxy compound (2) according to the present invention, X ¹ is a divalent linking group comprising a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -CO-, preferably a direct bond or a divalent hydrocarbon group having 1 to 13 carbon atoms. The divalent hydrocarbon group having 1 to 13 carbon atoms preferably includes an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably an optionally branched alkylene group having 1 to 10 carbon atoms. . X ¹ is more preferably a direct bond, a methylene group, or an isopropylidene group.
When multiple X ¹ 's exist in formula (2), the multiple X ¹ 's may be the same or different.

R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, It is a group selected from the group consisting of an alkynyl group having 1 to 12 carbon atoms and an OG group, and OG represents an unsubstituted glycidyl ether. Alkyl groups, alkoxy groups, aryl groups, alkenyl groups, and alkynyl groups may have substituents.

Examples of alkyl groups include the following.
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n- decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group and the like. .

Examples of alkoxy groups include the following.
For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, tert-pentoxy, cyclopentyl thoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethyl cyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group, benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, naphthylmethoxy group, phenethyloxy group, 2-phenylisopropoxy group, and the like.

Examples of alkenyl groups include the following.
For example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group groups, cinnamyl groups, naphthylvinyl groups, and the like.

Examples of alkynyl groups include the following.
Examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1,3-butandienyl, phenylethynyl, naphthylethynyl and the like.

Aryl groups include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, styryl group, xylyl group, n-propylphenyl group, isopropylphenyl group, mesityl group, ethynylphenyl group, A naphthyl group, a vinylnaphthyl group, and the like can be mentioned.

R ⁴ to R ¹⁵ are preferably each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably each independently a hydrogen atom or a carbon number 1 to 12 alkyl groups.

n in formula (2) is an integer of 0-10, preferably 0-5, more preferably 0-3.

The epoxy compound (2) is not particularly limited as long as it satisfies the formula (2), and commercially available epoxy resins can be used. Preferably, phenol novolak type epoxy resin, ortho cresol novolak type epoxy resin, xylenephenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin. Epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol G type epoxy resin, bisphenol TMC type epoxy resin, biphenol type epoxy resin, tetramethylbiphenol type epoxy resin , biphenyl-type epoxy resins, sulfur atom-containing epoxy resins, and the like. Phenol novolak type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable.

The amount of hydrolyzable chlorine in the epoxy compound (2) used in the present invention is preferably 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1700 ppm or less, and particularly preferably 1000 ppm or less. As this value becomes smaller, the electrical reliability of the electronic material can be improved. Incidentally, the amount of hydrolyzable chlorine in the epoxy compound (2) can be measured by the measuring method shown in Examples below.

[Content ratio of propenyl group-containing compound (1) and epoxy compound (2)]
The content ratio of the propenyl group-containing compound (1) and the epoxy compound (2) in the curable resin composition of the present invention is not particularly limited. Amount of substance)/(amount of substance of epoxy group in epoxy compound (2)) is preferably in the range of 0.1 to 10.0. This value is more preferably 0.2 to 5.0, particularly preferably 0.5 to 2.0. If this ratio is equal to or less than the above upper limit, the curable resin composition tends to be excellent in bending strength and fracture toughness, and if it is equal to or more than the above lower limit, it tends to be excellent in heat resistance.

Here, the hydroxyl group of the propenyl group-containing compound means all propenyl group-containing compounds contained in the curable resin composition of the present invention, that is, usually propenyl group-containing compound (1) and propenyl group-containing compound (1A). is the total hydroxyl group of The amount of substance is calculated by dividing the mass of the chemical structure containing the functional group in the curable composition by the molecular weight and multiplying the number of the functional group in the chemical structure.

The curable resin composition of the present invention may contain only one type of the propenyl group-containing compound (1), or may contain two or more types. Moreover, also about an epoxy compound (2), only 1 type may be contained and 2 or more types may be contained.

[Curing component]
In the curable resin composition of the present invention, maleimide is added to a total of 100 parts by mass of the propenyl group-containing compound (1) (which may be the propenyl group-containing compound (I)) and the epoxy compound (2). At least one selected from the group consisting of resins, phenol resins, benzoxazine resins, cyanate ester resins, active ester resins, resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins and carbodiimide resins (hereinafter referred to as these may be referred to as a "curing component".) preferably contains 0.01 to 1000 parts by mass, the content of these curing components is more preferably 0.1 to 500 parts by mass, and more It is preferably 1.0 to 300 parts by mass. If the content of the curing component is at least the above lower limit, a cured product with excellent heat resistance can be obtained. If the content of the curing component is equal to or less than the above upper limit, a cured product having excellent mechanical strength can be produced.

<Maleimide resin>
A maleimide resin is a maleimide compound having an average of one or more maleimide groups in one molecule. Examples of maleimide resins include bismaleimides having two maleimide groups in one molecule, polyphenylmethane maleimide, and the like.

Examples of bismaleimides include alkylbismaleimide, diphenylmethanebismaleimide, phenylenebismaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, and the like. 4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide-(2,2,4-trimethyl)hexane, 4,4′-diphenyletherbismaleimide, 4 ,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are linked via methylene groups.

Among the maleimide resins described above, 4,4′-diphenylmethanebismaleimide and polyphenylmethanemaleimide are preferred as the maleimide resin because of their excellent compatibility with the propenyl group-containing composition of the present invention and their relatively low cost. preferable.

A commercially available product may be used as the maleimide resin. Examples of commercially available maleimide resins include product name "BMI-1100" (4,4'-diphenylmethane bismaleimide) and product name "BMI-2300" (polyphenylmethane maleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. .

The maleimide resin may be used alone or in combination of two or more.

<Phenolic resin>
Examples of phenolic resins include phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and/or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and formaldehyde. , benzaldehyde, salicylaldehyde, and other compounds having an aldehyde group in the presence of an acidic catalyst to condense or co-condense novolac-type phenolic resins; phenols and/or naphthols and dimethoxyparaxylene or bis(methoxymethyl)biphenyl phenol-aralkyl resins synthesized from; aralkyl-type phenol resins such as biphenylene-type phenol-aralkyl resins and naphthol-aralkyl resins; Dicyclopentadiene-type phenolic resins such as diene-type phenolic novolac resins and dicyclopentadiene-type naphthol novolak resins; triphenylmethane-type phenolic resins; terpene-modified phenolic resins; para-xylylene and/or meta-xylylene-modified phenolic resins; modified phenolic resins; and phenolic resins obtained by copolymerizing two or more of these. However, the phenol resin referred to here does not include the propenyl group-containing compound (1) and the propenyl group-containing compound (1A).

A phenol resin may be used individually by 1 type, and may use 2 or more types together.

<Benzoxazine resin>
Benzoxazine resins include, for example, 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene) bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. The benzoxazine resin may contain a structure in which the oxazine ring is ring-opening polymerized.

The benzoxazine resins may be used singly or in combination of two or more.

<Cyanate ester resin>
Examples of cyanate ester resins include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′- ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl) Bifunctional cyanate resins such as methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene(benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether), phenolic novolacs and cresols Examples include polyfunctional cyanate resins derived from novolaks and the like, and prepolymers obtained by partially triazinizing these cyanate resins.

A cyanate ester resin may be used individually by 1 type, and may use 2 or more types together.

<Active ester resin>
The active ester resin is not particularly limited, but generally contains two highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having one or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.
Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m - cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine , benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester resin containing a dicyclopentadiene type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, and an active ester resin containing a benzoylated phenol novolak are preferred. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene-type diphenol structure are more preferable. Here, the "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

Active ester resin may be used individually by 1 type, and may use 2 or more types together.

<Resin having a radically polymerizable functional group>
Resins having a radically polymerizable functional group include resins having one or more ethylenically unsaturated groups having a carbon-carbon double bond in the molecule. The ethylenically unsaturated group is preferably one or more groups selected from the group consisting of acryl groups, methacryl groups, styryl groups, olefin groups and maleimide groups. Preferred examples of olefinic groups include allyl, vinyl and propenyl groups. Thus, in one preferred embodiment, the radically polymerizable functional group is one or more selected from the group consisting of acrylic groups, methacrylic groups, styryl groups, allyl groups, vinyl groups, propenyl groups and maleimide groups. However, the resin having a radically polymerizable functional group as used herein does not include the propenyl group-containing compound (1) and the propenyl group-containing compound (1A).

A resin having a radically polymerizable functional group may be used alone or in combination of two or more.

<Isocyanate resin>
Examples of isocyanate resins include resins having one or more isocyanate groups in the molecule. The isocyanate resin preferably has two or more isocyanate groups in its molecule. Examples of isocyanate resins include 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

The isocyanate resin may be used singly or in combination of two or more.

<Acid anhydride resin>
Acid anhydride resins include resins having one or more acid anhydride groups in the molecule. Examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetra Carboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3- Examples include polymer-type acid anhydrides such as dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid.

The acid anhydride resin may be used alone or in combination of two or more.

<Carbodiimide resin>
Carbodiimide resins include resins having one or more carbodiimide groups (-N=C=N-) in the molecule. The carbodiimide resin preferably has two or more carbodiimide groups in its molecule. Specific examples of carbodiimide resins include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

Carbodiimide resin may be used individually by 1 type, and may use 2 or more types together.

Among these, maleimide resin is preferable as the curing component. Moreover, when a maleimide resin is used, it is preferably a maleimide resin having a maleimide equivalent of 120 to 300 g/eq.

[Other ingredients]
The curable resin composition of the present invention may contain one or more other components in addition to the propenyl group-containing compound (1), the epoxy compound (2), and the above curing component. Other components include curing accelerators, inorganic fillers, solvents, release agents, surface treatment agents, colorants, thermoplastic polymers, organic fillers, flame retardants, and the like.

As the curing accelerator, a curing accelerator that accelerates the curing reaction between the propenyl group-containing compound (1) and the maleimide resin (hereinafter also referred to as "curing accelerator (P)"), , a curing accelerator (hereinafter also referred to as “curing accelerator (Q)”) that accelerates the curing reaction between the propenyl group-containing compound (1) and the epoxy compound (2).

Examples of curing accelerators (P) include imidazoles and organic peroxides. When imidazoles are used as the curing accelerator (P), the curing reaction between the propenyl group-containing compound (1) and the epoxy compound (2) is also accelerated.

Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-unde__cylimidazole, 2-heptadecylimidazole, 2-phenyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl- 2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole.

Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters.

As the curing accelerator (P), those that are relatively stable at high temperatures, have good solvent solubility, and are easy to handle are preferable. Among imidazoles, 2-ethyl-4-methylimidazole and organic peroxides are used. Dicumyl peroxide of dialkyl peroxide is preferred.

These curing accelerators (P) may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains the curing accelerator (P), its content is preferably 0.1 to 5.0% by mass relative to the maleimide resin.

The curing accelerator (Q) is not particularly limited, and examples thereof include phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, and amine complex salts.

Phosphorus compounds include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, triphenyl phosphite and the like.
Tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo[5.4.0]undecene-7 and the like.

As the curing accelerator (Q), phosphorus-based compounds, particularly triphenylphosphine, are preferable because they have excellent curability, heat resistance, and electrical properties, and are less susceptible to deterioration in humidity resistance reliability.

These curing accelerators (Q) may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains the curing accelerator (Q), its content is preferably 0.1 to 5% by mass relative to the epoxy compound (2).

Examples of inorganic fillers include crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. Among these, crystalline silica powder and fusible silica powder are preferred. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

When the curable resin composition of the present invention contains an inorganic filler, the content thereof is preferably 30 to 90% by mass with respect to the entire curable resin composition.

When the curable resin composition of the present invention is used as a thermosetting molding material for forming a sealing material, the curable resin composition of the present invention preferably contains a curing accelerator and an inorganic filler.

The curable resin composition of the present invention can be made into a resin varnish by blending a solvent and dissolving a curing component such as a maleimide resin or a resin having a radically polymerizable functional group in the solvent. The solvent is not particularly limited as long as it dissolves the propenyl group-containing compound (1), the epoxy compound (2), the curing component, etc. Typically, a polar solvent is used. Examples of the polar solvent include those mentioned in the description of the propenylation reaction. A solvent may be used individually by 1 type, and may use 2 or more types together.

The resin varnish contains propenyl group-containing compound (1) and epoxy compound (2), a curing component such as a maleimide resin, and a solvent as essential components. Laminates such as laminates can be manufactured.

The content of the solvent in the resin varnish is appropriately set according to the solid content concentration of the resin varnish. The solid content concentration of the resin varnish varies depending on the application, but is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
The solid content concentration of the resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.

The resin varnish comprises a curing component such as a maleimide resin or a resin having a radically polymerizable functional group, a propenyl group-containing compound (1) and an epoxy compound (2), other components blended as necessary, and a solvent. can be produced by mixing Mixing of each component can be performed by a conventional method.

Examples of release agents include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents.
Carbon black etc. are mentioned as a coloring agent.

Thermoplastic polymers include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Ether ether ketone resins, polyether imide resins, silicone resins, tetrafluoroethylene resins and the like can be mentioned.

Organic fillers include, for example, polyethylene, polypropylene, polystyrene, polyphenylene ether resins, silicone resins, tetrafluoroethylene resin fillers having a uniform structure, acrylic acid ester resins, methacrylic acid ester resins, and conjugated diene resins. A resin filler having a core-shell structure having a rubber-like core layer made of, etc., and a glass-like shell layer made of an acrylic acid ester-based resin, a methacrylic acid ester-based resin, an aromatic vinyl-based resin, a vinyl cyanide-based resin, etc. is mentioned.

Flame retardants include, for example, halogen-containing flame retardants containing bromine and chlorine; triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, red phosphorus and other phosphorus-based flame retardants; sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide;

[Method for producing curable resin composition and viscosity modifier]
Regarding the method for producing the curable resin composition of the present invention, the compounds and resins described above may be mixed separately. , an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, an acid anhydride resin, and a carbodiimide resin. Compound (1) (which may be a propenyl group-containing compound (I)) is mixed to obtain a curable resin composition, from the viewpoint of adjusting the viscosity of the resulting curable resin composition and improving handling properties. preferable.

That is, the group consisting of an epoxy compound (2), a maleimide resin, a phenol resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, an acid anhydride resin and a carbodiimide resin. A mixture containing at least one curing component selected from the above can be used as a viscosity modifier for adjusting the viscosity of the curable resin composition. Moreover, among these, the viscosity modifier containing the mixture containing an epoxy compound (2) and a maleimide resin is preferable.

In this case, the mixing ratio of the curing component such as the maleimide resin and the epoxy compound (2) is not particularly limited. The value is preferably in the range of 0.01 to 100.0, more preferably 0.1 to 10.0, particularly preferably 0.2 to 5.0. If this ratio is equal to or less than the above upper limit, the viscosity of the mixture as a viscosity modifier does not increase excessively, and if it is equal to or more than the above lower limit, it is possible to prevent deterioration of the heat resistance of the obtained cured product. .

In particular, the propenyl group-containing compound (1) (which may be the propenyl group-containing compound (I)) is added to the mixture as a viscosity modifier rather than in a single state to reduce or control the viscosity. can be easily performed, so it is preferable.

When mixing the epoxy compound (2) and a curing component such as a maleimide resin, the viscosity of each component is high at room temperature, and it takes a long time to mix with the curing component. preferably. This heating and melting is preferably carried out at 40 to 150° C. for about 1 to 60 minutes.

The melt viscosity at 150° C. of the viscosity modifier comprising a mixture of the epoxy compound (2) and a curing component such as a maleimide resin is preferably 0.01 to 1.6P, more preferably 0.05 to 1.2P. , more preferably 0.1 to 1.0P. When the melt viscosity is equal to or less than the above upper limit, the viscosity is low, and mixing with the propenyl group-containing compound (1) and the like becomes easy. When the melt viscosity is at least the above lower limit, bleeding out is less likely to occur during molding into a mold or the like.
The melt viscosity is measured by the method described in the Examples section below.

The gel time at 175°C of the viscosity modifier comprising a mixture of the epoxy compound (2) and a curing component such as a maleimide resin is preferably 100 seconds or longer, more preferably 120 seconds or longer, and still more preferably 180 seconds or longer. Most preferably, it does not gel. If the gel time is at least the above lower limit, mixing with other components will be facilitated, contributing to improved productivity.
This gel time is measured by the method described in the section of Examples below.

Among them, the curing component used in the viscosity modifier is preferably a maleimide resin, and as the maleimide resin, a maleimide resin having a maleimide equivalent of 120 to 300 g/eq is preferable as described above.

[Curing and application of curable resin composition]
Curing of the curable resin composition of the present invention is preferably carried out by controlling the curing temperature to 150 to 250°C. An example of the curing operation includes a method of once curing at the suitable curing temperature for 30 seconds or more and 3 hours or less, and then post-curing at the suitable curing temperature for 1 to 20 hours. .

Applications of the curable resin composition of the present invention will be described in detail later. Examples include various coating agents, adhesives, build-up laminate materials, fiber reinforced plastics (FRP), and the like.

The curable resin composition of the present invention may be used after being cured for these uses, or may be used after being cured in the manufacturing process for these uses.

[Cured product]
The cured product of the present invention can be obtained by curing the curable resin composition of the present invention. The cured product of the present invention obtained by curing the curable resin composition of the present invention has excellent crack resistance, mechanical strength, and adhesion to metals.

The method for curing the curable resin composition of the present invention is not particularly limited, but usually a cured product can be obtained by a thermosetting reaction by heating. During the thermosetting reaction, it is preferable to appropriately select the curing temperature depending on the type of curing component used. For example, when a maleimide resin is used, the curing temperature is usually 80 to 250.degree. By adding a curing accelerator to these curing components, it is also possible to lower the curing temperature. The curing reaction time is preferably 0.5 to 20 hours, more preferably 1 to 18 hours, still more preferably 2 to 15 hours. When the reaction time is at least the above lower limit, the curing reaction tends to proceed sufficiently, which is preferable. On the other hand, when the reaction time is equal to or less than the above upper limit, it is preferable because thermal deterioration due to heating and energy loss during heating can be easily reduced.

[Use]
The curable resin composition of the present invention is excellent in curability, and the cured product using the curable resin composition of the present invention is excellent in mechanical strength and adhesive strength to metal.

Therefore, the curable resin composition and the cured product thereof of the present invention can be effectively used in any application as long as these physical properties are required. For example, coating fields such as optical materials, automotive coatings such as automotive electrodeposition coatings, heavy anticorrosion coatings for ships and bridges, and coatings for the inner surface of beverage cans; composite materials, laminates, semiconductor sealing materials, liquid insulation Electrical and electronic fields such as sealing materials, insulating powder coatings, coil impregnation; seismic reinforcement of bridges, concrete reinforcement, building flooring, lining of water supply facilities, drainage and permeable pavement, adhesives for structures, vehicles and aircraft It can be suitably used for any application in the fields of civil engineering, construction, adhesives, and the like. Among these, it is particularly useful for electrical and electronic parts.

[Laminate]
As a method for producing a laminate using the curable resin composition of the present invention, a laminate containing a prepreg in which a fibrous base material is impregnated with the resin varnish made of the curable resin composition of the present invention is heated and pressurized. a method of producing a laminate by curing with a heat.

More specifically, a fibrous base material is impregnated with a resin varnish, dried, and the solvent is removed to obtain a prepreg. This prepreg is laminated with another base material to be used as necessary to form a laminate, and the laminate is cured by heating and pressurization to obtain a laminate.

The number of prepreg layers in the laminate may be one, or two or more. In the laminate, other base material than prepreg may be laminated. Other substrates include, for example, metal foils such as copper foils.

Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fiber, carbon fiber, ceramic fiber and stainless steel fiber; natural fibers such as cotton, hemp and paper; synthetic organic fibers such as polyester resin and polyamide resin. mentioned. Any one of these fibers may be used alone, or two or more thereof may be used in combination.

The shape of the fibrous base material is not particularly limited, and examples thereof include staple fiber, yarn, mat and sheet.

The amount of the resin varnish with which the fibrous base material is impregnated is not particularly limited, and for example, the solid content of the resin varnish to be impregnated is about 30 to 50% by mass with respect to the fibrous base material (100% by mass). make it
The heating temperature for heating and pressurizing the laminate is preferably the curing temperature described above. The pressurization conditions are preferably 2 to 20 kN/m ² .

A laminate manufactured in this manner comprises a fiber-reinforced resin layer containing a fibrous base material and a cured resin varnish. The number of fiber-reinforced resin layers included in the laminate may be one or two or more. As mentioned above, the laminate may have a metal foil layer, such as a copper foil.

[Sealant]
When the curable resin composition of the present invention is used as a sealing material, the shape of the sealing material to which the curable resin composition of the present invention is applied is not particularly limited. A shape similar to the shape can be adopted.
Examples of the method of forming a sealing material using the curable resin composition of the present invention include a method of sealing a semiconductor using a transfer molding method, a compression molding method, or the like.

EXAMPLES The content of the present invention will be described in more detail below using examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention. It may be a range defined by a value in an example or a combination of values between examples.

[Materials used]
The compounds and resins used in the following examples and comparative examples are as follows.
The amount of hydrolyzable chlorine in the epoxy resin used was measured by the following method.

<Hydrolyzable chlorine content>
0.5 g of epoxy resin was dissolved in 20 mL of dioxane, refluxed with 5 mL of 1N KOH/ethanol solution for 30 minutes, and then titrated with 0.01N silver nitrate solution for quantification.

- Maleimide resin: polyphenylmethane maleimide represented by the following structural formula ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide equivalent: 179 g / eq)

- Propenylphenol resin: propenylphenol represented by the following structural formula (1-1) (manufactured according to Synthesis Example 1)

Epoxy resin: bisphenol A type epoxy resin represented by the following structural formula ("jER (registered trademark) 828US" manufactured by Mitsubishi Chemical Corporation, hydrolyzable chlorine content: 700 ppm) (described as "828" in Tables 1 and 2) do.)

Epoxy resin: Bisphenol F type epoxy resin represented by the following structural formula ("jER (registered trademark) 806H" manufactured by Mitsubishi Chemical Corporation, hydrolyzable chlorine content: 1200 ppm) (described as "806H" in Tables 1 and 2) do.)

Epoxy resin: phenolic novolak type epoxy resin represented by the following structural formula ("jER (registered trademark) 152" manufactured by Mitsubishi Chemical Corporation, a mixture of n = 0 to 3, hydrolyzable chlorine content: 1300 ppm) (Table 1, 2, described as "152".)

・Curing accelerator: Triphenylphosphine

[Synthesis Example 1: Production of propenylphenol]
<Allylation>
840 mL of N,N-dimethylformamide, 575 g (7.51 mol) of allyl chloride, 1245 g (9.01 mol) of potassium carbonate, and 280 g (1.50 mol) of biphenol were added to a 10 L autoclave, sealed, and heated to 40°C. The temperature was raised to 65° C. over 1 hour. After aging at 65° C. for 5 hours, it was cooled to room temperature and the autoclave was opened. 1678 g of water and 1600 g of methyl isobutyl ketone were added thereto to dissolve the inorganic salt and crystals, and the aqueous layer was removed by liquid separation. After repeating the operation of adding 1678 g of water to the remaining methyl isobutyl ketone layer and washing with water at 60° C. three times, methyl isobutyl ketone is distilled off to obtain a compound represented by the following formula (A) (hereinafter referred to as “compound (A )” was obtained.

<Claisen rearrangement reaction>
165 g (620 mmol) of compound (A) and 825 mL of N,N-diethylaniline were placed in a 2 L four-necked flask, heated at 200° C. for 6 hours, and then cooled to room temperature. Subsequently, 495 mL of water and 149 mL (1.86 mol) of a 50% by mass sodium hydroxide aqueous solution were placed in a 2 L separable flask and cooled to 10° C., then the above N,N-diethylaniline solution was added dropwise and stirred for 30 minutes. After that, the mixture was allowed to stand, and the upper layer and the lower layer were extracted. Next, 495 mL of water and 93.1 g (1.86 mol) of concentrated sulfuric acid were placed in a 2 L separable flask and cooled to 10° C., and the lower layer extracted in the previous operation was added dropwise and stirred for 1 hour. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure. )”) was obtained (1.19 mol, two-step yield 80.4%).

<Propenylation>
100 parts by mass of compound (1A-1) and 100 parts by mass of methanol were charged into a reaction vessel, stirred and dissolved, and then 79 parts by mass of granular potassium hydroxide (purity 85%) were added. After the addition, methanol was distilled off while heating, and the reaction was carried out for 4 hours while maintaining the internal temperature at 100°C. Then, 203 parts by mass of methyl isobutyl ketone was added, neutralized with sulfuric acid, and washed with water repeatedly. Then, methyl isobutyl ketone is distilled off from the oil layer under heating at 120° C. under reduced pressure to obtain a propenyl group-containing compound (1) having a structure represented by the formula (1-1) (hereinafter referred to as “compound (1 -1)".

[Examples 1 to 5, Comparative Example 1]
Epoxy resin and maleimide resin were weighed at the ratios shown in Table 1, heated at 100° C. for 15 minutes, and subjected to melting treatment to obtain respective viscosity modifiers. Melt viscosity (ICI viscosity) and gel time of the obtained viscosity modifier were measured by the following methods. Table 1 shows the results.

<ICI viscosity>
The ICI viscosity of the viscosity modifier was measured using a cone plate viscometer (CV-1 manufactured by Toa Kogyo Co., Ltd.) heated to 150°C.
<Gel Time>
The viscosity modifier was heated to 175° C. with a gel time tester (BIG HEART manufactured by Imoto Seisakusho Co., Ltd.), and the time until gelation was measured on a hot plate.

[Examples 6 to 8, Comparative Example 2]
An epoxy resin and a maleimide resin were mixed at the ratios shown in Table 2 to obtain viscosity modifiers.
Separately, a curing accelerator was added to the propenylphenol produced in Synthesis Example 1 to obtain a propenylphenol-containing composition.
Thereafter, the viscosity modifier and the propenylphenol-containing composition were mixed to obtain a curable resin composition.
This curable resin composition was poured into an aluminum casting mold and cured at 120° C. for 2 hours and then at 200° C. for 6 hours to prepare a cured product.

The bending strength and fracture toughness values of the resulting cured product were measured and calculated by the methods described below.
Also, using the obtained curable resin composition, a shear adhesion test piece to metals (copper and aluminum) was produced by the method shown below, and the adhesion strength was measured.
These results are shown in Table 2.

<Hardened product: bending strength>
The flexural strength was measured by preparing a rectangular test piece (60 x 10 x 3 mm) according to JIS K6911, using a material universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) at a load rate of 1.5 mm / min. The distance between fulcrums was 48 mm, and the measurement was performed by the three-point bending method. Bending strength (σ) and bending elastic modulus (E) were calculated according to the following formulas.
σ=3PL/2Wh ²
E = (L3/ ^4Wh3 ) x ⁽ F/Y)
P: Maximum load W: Width of test piece h: Thickness of test piece L: Distance between fulcrums F/Y: Slope of the initial linear portion in the stress-strain curve

<Hardened product: Fracture toughness value>
The fracture toughness value was measured by a three-point bending method using a rectangular test piece (46 x 10 x 3 mm) according to ASTM D5045-93 and using a universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation). It was measured. A groove was previously made in the test piece with a cutting machine, and a microtome blade was applied to the bottom of the groove and hit with a hammer to form a notch crack. The measurement was performed at a load rate of 1 mm/min and a distance between fulcrums of 40 mm, and the critical stress intensity factor (KIC) was calculated according to the following formula and used as the fracture toughness value.
KIC = (PS/ ^BW3 /2) x f(x)
f(x)=3x ^1/2 {1.99−x(1−x)(2.15−3.93x+2.7x ² )/{2(1+2x)(1−x) ^3/2 }
x=a/W (0.45<x<0.55)
P: Maximum load S: Distance between fulcrums B: Thickness of test piece W: Width of test piece a: Crack length

<Curable resin composition: shear adhesive strength to metal>
It was implemented according to JIS K6850. That is, the curable resin composition was applied between two metal pieces each having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm so as to have a width of 25 mm, a length of 12.5 mm, and a thickness of 100 μm. After coating, the coating was placed in a constant temperature bath and cured at 120° C. for 2 hours and at 200° C. for 6 hours to prepare peel test pieces.
The metal pieces used in the shear adhesion test were a copper plate (both sides sandblasted), a copper plate (both sides smoothed), an aluminum plate (both sides sandblasted), and an aluminum plate (both sides smoothed). I used the one made by
The prepared peel test piece was subjected to a tensile shear test using a material universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) at a speed of 5 mm / min with a number of tests n = 3, and the tensile shear strength was measured. was measured and the average value was obtained.

[Evaluation of results]
From Table 1, the viscosity modifiers of Examples 1 to 5 have improved fluidity and a longer gelation time than the maleimide resin alone of Comparative Example 1. Therefore, the epoxy compound (2) and the maleimide resin are mixed. Therefore, it can be seen that there is an advantage that industrial handleability is improved. From this result, it is predicted that gelation does not progress even when mixed with a curing component other than the maleimide resin, and that the properties are advantageous in terms of the production method as well.
Further, from Table 2, in Examples 6 to 8, the epoxy compound (2) of Comparative Example 2 was used as the cured product using the viscosity modifier containing the epoxy compound (2) and the propenyl group-containing compound (1). It can be seen that the flexural strength, fracture toughness, and adhesive strength to metal are superior to those of the cured product without the adhesive.

Claims (6)

A curable resin composition comprising a propenyl group-containing compound represented by the following formula (1) and an epoxy compound represented by the following formula (2).

(In formula (1) above, X is a divalent linking group, which is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S—, or carbon number an aliphatic hydrocarbon group of 1 to 20. R ¹ and R ² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.) To a total of 100 parts by mass of the propenyl group-containing compound represented by the formula (1) and the epoxy compound represented by the formula (2), maleimide resin, phenol resin, benzoxazine resin, cyanate ester resin, active ester resin , 0.01 to 1000 parts by mass of at least one selected from the group consisting of resins having radically polymerizable functional groups, isocyanate resins, acid anhydride resins and carbodiimide resins. The curable resin composition according to claim 1. thing. A cured product obtained by curing the curable resin composition according to claim 1 or 2. An electric/electronic component comprising the cured product according to claim 3. An epoxy compound represented by the following formula (2), a maleimide resin, a phenol resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, an acid anhydride resin, and a carbodiimide. and at least one selected from the group consisting of resins.

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.) An epoxy compound represented by the following formula (2), a maleimide resin, a phenol resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, a resin having a radically polymerizable functional group, an isocyanate resin, an acid anhydride resin, and a carbodiimide. A curable resin composition obtained by mixing in advance with at least one selected from the group consisting of resins, and then mixing the mixture with a propenyl group-containing compound represented by the following formula (1) to obtain a curable resin composition. Production method.

(In formula (1) above, X is a divalent linking group, which is a direct bond, —SO ₂ —, —O—, —CO—, —C(CF ₃ ) ₂ —, —S—, or carbon number an aliphatic hydrocarbon group of 1 to 20. R ¹ and R ² are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, and may be the same or different.)

(In formula (2) above, X ¹ is a divalent linking group, a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, — C(CF ₃ ) ₂ — or —CO—, and R ⁴ to R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. is a group selected from the group consisting of 12 aryl groups, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms and OG groups, n represents an integer of 0 to 10. OG is an unsubstituted represents a glycidyl ether group.)