JP2021116427A - Propenyl group-containing composition, curable resin composition, cured product, and electric and electronic components - Google Patents

Abstract

To provide: a propenyl group-containing composition which has low viscosity and can form a cured product excellent in heat resistance and long-term reliability; and a curable resin composition based on the same.SOLUTION: The propenyl group-containing composition comprises a compound represented by the formula (1) in the figure, where the content of the compound represented by the formula (1) is 80.0 to 99.9 mass%. The curable resin composition contains 0.01 to 1000 pts.mass of one or more selected from the group consisting of epoxy resins, maleimide resins and phenol resins, based on 100 pts.mass of the propenyl group-containing composition.SELECTED DRAWING: None

Description

The present invention relates to propenyl group-containing compositions, curable resin compositions, cured products and electrical / electronic components.

The thermosetting resin composition utilizes its curability and is used in various fields as a thermosetting molding material and the like. Examples thereof include adhesives and encapsulants for electrical and electronic components.

As a thermosetting resin composition, a resin composition obtained by mixing a maleimide resin or an epoxy resin with allylphenol, alkenylphenol, alkenylphenol ether or the like has been proposed.

For example, Patent Document 1 and Patent Document 2 disclose a composition composed of a mixture of bismaleimide and amine, alkenylphenol, alkenylphenol ether, etc., and the alkenylphenol is produced by rearrangement of allyl ether of phenol. Is disclosed.

Further, Patent Document 3 describes, as a resin composition having excellent heat resistance, low water absorption, and capable of suppressing voids in a cured product, a specific propenyl group-containing resin having a benzene ring having a propenyl group or a naphthalene ring, and 1 A resin composition containing a maleimide compound having two or more maleimide groups in the molecule is disclosed.

Japanese Unexamined Patent Publication No. 62-181335 JP-A-4-227931 Japanese Unexamined Patent Publication No. 2019-0119149

In the past, most semiconductors were used with relatively small currents and electric power such as LSIs, but in recent years, the development of power semiconductors and the like that use semiconductors for controlling motors and lighting and converting electric power is rapid. It is proceeding to. Along with this, semiconductors and semiconductor encapsulants that can be used for higher power and current than before have been sought, and semiconductor encapsulants have higher heat resistance, lower viscosity, and longer-term reliability than conventional ones. Is required.

A cured product obtained by curing a resin composition containing a propenyl group-containing resin and a maleimide compound described in Patent Document 3 has heat resistance, low viscosity, and long-term as a semiconductor encapsulant used for the above-mentioned applications. I was not satisfied with the reliability.

The present invention comprises a propenyl group-containing composition capable of providing a curable resin composition having a low viscosity and excellent heat resistance and long-term reliability, a curable resin composition using the same, and a curable resin composition thereof. The purpose is to provide cured products and electrical / electronic parts.

As a result of diligent studies to solve the above problems, the present inventor pays attention to the temperature range of the curing start of the curing reaction of the maleimide resin, and controls the curing start temperature to carry out the curing reaction at a low temperature. However, based on the speculation that low viscosity and long-term reliability can be achieved while exhibiting high heat resistance, the skeleton and purity of the propenyl group-containing compound blended with the maleimide resin are important for controlling the curing start temperature. We found that it could be a regulator. Then, they have found that a specific propenyl group-containing composition can achieve low viscosity and long-term reliability while exhibiting high heat resistance even when the curing temperature is lowered, and have completed the present invention.

That is, the gist of the present invention lies in the following [1] to [8].

[1] A propenyl group-containing composition containing a compound represented by the following formula (1), wherein the content of the compound represented by the formula (1) is 80.0 to 99.9% by mass. Propenyl group-containing composition.

(In the above formula (1), X is a direct bond, -SO _2- , -O-, -CO-, -C (CF ₃ ) _2- , -S- and an aliphatic hydrocarbon having 1 to 20 carbon atoms. It is a divalent linking group selected from the groups. R ¹ and R ² are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms or halogen atoms, and may be the same or different from each other.)

[2] The propenyl group-containing composition according to [1], which contains 0.1 to 20.0% by mass of a compound represented by the following formula (2).

(In the above formula (2), X, R ¹ , and R ² are synonymous with those in the above formula (1).)

[3] The propenyl group according to [1] or [2], wherein the proportion of the trans compound in which the propenyl group is all trans type among the compounds represented by the formula (1) is 20 to 95%. Composition.

[4] The propenyl according to any one of [1] to [3], wherein the proportion of cis-forms in which all propenyl groups are cis-type among the compounds represented by the formula (1) is 30% or less. Group-containing composition.

[5] The propenyl group-containing composition according to any one of [1] to [4], wherein the melt viscosity at 150 ° C. is in the range of 0.01 to 10.0 P.

[6] Epoxy resin, maleimide resin, phenol resin, benzoxazine resin, cyanate ester resin, active ester resin, radical polymerization with respect to 100 parts by mass of the propenyl group-containing composition according to any one of [1] to [5]. A curable resin composition containing 0.01 to 1000 parts by mass of at least one selected from the group consisting of a resin having a sex functional group, an isocyanate resin, an acid anhydride resin and a carbodiimide resin.

[7] A cured product obtained by curing the curable resin composition according to [6].

[8] An electrical / electronic component containing a cured product of the curable resin composition according to [6].

The curable resin composition of the present invention obtained by mixing the propenyl group-containing composition of the present invention with a maleimide resin, an epoxy resin, or the like provides a cured product having a low viscosity, high heat resistance, and excellent long-term reliability. Can be done.
Therefore, according to the propenyl group-containing composition and the curable resin composition of the present invention, the electrical reliability is excellent, the heat-resistant decomposition property, the adhesive property, the low hygroscopicity, the low elasticity, and the change in the physical properties under a high temperature region are observed. It is possible to provide a small amount of highly reliable cured product and electrical / electronic parts.

The 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 as long as the gist of the present invention is not exceeded. do not have. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

[Propenyl group-containing composition]
The propenyl group-containing composition of the present invention contains a compound represented by the following formula (1), and the content of the compound is 80.0 to 99.9% by mass.

(In the above formula (1), X is a direct bond, -SO _2- , -O-, -CO-, -C (CF ₃ ) _2- , -S- and an aliphatic hydrocarbon having 1 to 20 carbon atoms. It is a divalent linking group selected from the groups. R ¹ and R ² are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms or halogen atoms, and may be the same or different from each other.)

The propenyl group-containing composition of the present invention includes a compound represented by the above formula (1) (hereinafter, may be referred to as "propenyl group-containing compound (1)") and other optional components (for example, "propenyl group-containing compound (1)"). Since it contains a compound represented by the formula (2) described later, it is defined as a "propenyl group-containing composition", but in the technical field of the compound, the "propenyl group-containing compound" is composed of a single component. Other than that, it may be obtained as a "composition" composed of multiple components. Therefore, the propenyl group-containing composition of the present invention is expressed in the art as a "propernyl group-containing compound" (sometimes referred to as a "propenyl group-containing resin") or a "propernyl group-containing compound" ("propernyl group-containing compound". It may also be referred to as a "propenyl group-containing resin").

<Propenyl group-containing compound (1)>
In the above formula (1) representing the propenyl group-containing compound (1), the aliphatic hydrocarbon group having 1 to 20 carbon atoms of X is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably carbon. Examples thereof include an alkylene group which may have a branch of several 1 to 10. X is preferably a direct bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a direct bond, a methylene group, or an isopropylidene group, and most preferably X is a direct bond.

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

The propenyl group-containing compound (1) represented by the formula (1) is a cis-trans isomer of a double bond of a propenyl group (1-propenyl group) bonded to each of two benzene rings. Is included, and a "trans isomer" in which both of the two propenyl groups in the formula (1) are of the trans type and a "cis isomer" in which both of them are of the cis type are included.

The proportion of the trans form in the propenyl group-containing compound (1) is preferably 20 to 95%, more preferably 30 to 85%, still more preferably 45 to 75%. The larger the proportion of the transformer, the higher the crystallinity and the better the handleability in powder, and the smaller the ratio, the better the solubility in the solvent.

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

Further, the propenyl group-containing compound (1) includes other propenyl group-containing compounds (1) that do not belong to the trans form or the cis form. One of the two propenyl groups in the formula (1) is of the trans type and the other is of the cis type, and is usually contained in the propenyl group-containing compound (1) in an amount of about 5 to 50%.

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

The propenyl group-containing composition of the present invention contains the propenyl group-containing compound (1) in an amount of 80.0 to 99.9% by mass. When the content of the propenyl group-containing compound (1) in the propenyl group-containing composition of the present invention 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). The effect of is not fully obtained. Propenyl group-containing compound (1) Since it is practically difficult to produce a propenyl group-containing composition composed of 100% by mass, the content of the propenyl group-containing compound (1) in the propenyl group-containing composition of the present invention is usually used. Is 99.9% by mass or less. From the viewpoint of solubility in a solvent, the content of the propenyl group-containing compound (1) in the propenyl group-containing composition of the present invention is preferably 85. It is 0 to 99.8% by mass, more preferably 90.0 to 99.5% by mass.

In the propenyl group-containing composition of the present invention, the propenyl group-containing compound (2) described later remains in the propernylation reaction for producing the propenyl group-containing compound (1). The content of the propenyl group-containing compound (1) and the propenyl group-containing compound (2) described later can be controlled by, for example, changing the amount of the solvent in the propenylation reaction.
That is, in order to reduce the propenyl group-containing compound (1) and increase the propenyl group-containing compound (2), for example, it can be controlled by increasing the amount of the solvent, and conversely, the propenyl group-containing compound (1) is increased and propenyl. To reduce the group-containing compound (2), for example, it can be controlled by reducing the amount of the solvent.

The propenyl group-containing composition of the present invention is substantially composed of a propenyl group-containing compound (1) and a propenyl group-containing compound (2) described later, and contains a trace amount of impurities during the production of the propenyl group-containing compound (1). However, the total content of the propenyl group-containing compound (1) and the propenyl group-containing compound (2) in the propenyl group-containing composition shall be 70% by mass or more, particularly 80 to 100% by mass. Is preferable. The unavoidable impurities in the production of the propenyl group-containing compound (1) can be reduced by purifying the obtained propenyl group-containing composition by washing with water, chromatographic separation, crystallization and the like.

<Propenyl group-containing compound (2)>
The propenyl group-containing composition of the present invention may be described as a compound having a 2-propenyl group (allyl group) represented by the following formula (2) (hereinafter, "propenyl group-containing compound (2)"). ) Is preferably contained in an amount of 0.1 to 20.0% by mass.

(In the above formula (2), X, R ¹ , and R ² are synonymous with those in the above formula (1).)

In the propenyl group-containing composition of the present invention, the greater the amount of the propenyl group-containing compound (2), the lower the melt viscosity tends to be, and the less the propenyl group-containing composition, the longer the curing time of the curable resin composition containing the propenyl group-containing composition. Tends to be long. From this point of view, the content of the propenyl group-containing compound (2) in the propenyl group-containing composition of the present invention is preferably 0.2 to 10.0% by mass, more preferably 0.3 to 5. It is 0% by mass.

<Melting viscosity>
The propenyl group-containing composition of the present invention preferably has a melt viscosity at 150 ° C. of 0.01 to 10.0 P, more preferably 0.05 to 5 P, and even more preferably 0.1 to 3 P. When the melt viscosity is not more than the above upper limit value, the viscosity is low, so that it can be easily mixed with a maleimide resin, an epoxy resin, or the like described later. If the melt viscosity is equal to or higher than the above lower limit, bleed-out is unlikely to occur when molding into a mold or the like.
The melt viscosity of the propenyl group-containing composition is measured by the method described in the section of Examples described later.

<Softening point>
The softening point of the propenyl group-containing composition of the present invention is preferably 30 to 100 ° C, more preferably 35 to 80 ° C, and even more preferably 40 to 70 ° C. If the softening point is at least the above lower limit value, blocking is unlikely to occur, and if it is at least the above upper limit value, it flows in a short time during heating.
The softening point of the propenyl group-containing composition is measured by the method described in the section of Examples described later.

<Manufacturing of propenyl group-containing composition>
The method for producing the propenyl group-containing composition of the present invention is not particularly limited, but for example, it is abbreviated as "divalent phenol compound (3)" represented by the following formula (3). ) Is allylated to obtain an allyloxy group-containing compound represented by the following formula (4) (hereinafter, may be abbreviated as “allyloxy group-containing compound (4)”), and then allyloxy group-containing compound is obtained. The allyl group of the compound (4) is transferred to obtain the above-mentioned propenyl group-containing compound (2), and the allyl group of the propenyl group-containing compound (2) is changed to a 1-propenyl group to obtain the propenyl group-containing composition of the present invention. There is a method of making things.

(The above formula (3), (4), ^X, R 1, ^{R 2} have the same meanings as in the formula (1).)

As a method for allylating the divalent phenol compound (3), for example, the divalent phenol compound (3) is reacted with allyl halide, and at least a part of the hydroxyl groups are allyl etherified to form -O-CH _2-CH. = A method of converting to _{CH 2 can be mentioned.}

In this reaction, using 2.0 to 8.0 times the molar amount of the allyl halide with respect to the divalent phenol compound (3), particularly 3.0 to 6.0 times the molar amount, allows the reaction to proceed efficiently. , Preferable from the viewpoint of suppressing production costs.

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

Examples of the catalyst for the allyl etherification reaction include alkali metals such as sodium hydroxide, potassium hydroxide and potassium carbonate, amines such as diazabicyclononen, diazabicycloundecene and triethylamine, sodium tert-butoxide and potassium. Examples thereof include tert-butoxide, lithium diisopropylamide, silicon-basic amine, lithium tetramethylpiperidin and the like. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferable because they are relatively inexpensive and side reactions are unlikely to occur. One type of catalyst may be used alone, or two or more types may be used in combination.

The amount of the catalyst used in the allyl etherification reaction is preferably 0.7 to 2.0 times by mole, more preferably 0.8 to 1.5 times by mole, based on the amount of allyl halide used. If the amount of the catalyst used is too small, the reaction rate will be slow, and if the amount used is too large, excess alkali must be removed, resulting in a decrease in productivity.

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 for the propenylation reaction described later.

The reaction temperature of the allyl etherification reaction is not particularly limited as long as it is the temperature at which the hydroxyl group of the divalent phenol compound (3) reacts with the allyl halide, and is preferably 10 to 150 ° C, preferably 40 to 130 ° C.

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.) and the like.

The allyl group transfer of the allyloxy group-containing compound (4) obtained by allylation of the divalent phenol compound (3) is, for example, a Claisen rearrangement reaction by heating the allyloxy group-containing compound (4) after the allylation reaction. Can be carried out at. _{By 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.

The Claisen rearrangement reaction may be carried out according to a conventional method. For example, the allyloxy group-containing compound (4) may be subjected to the presence of a high boiling point solvent such as carbitol, paraffin oil, N, N'-dimethylaniline, N, N'-diethylaniline or the like. Heat in solvent-free. The solvent is used as needed in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the allyloxy group-containing compound (4). After completion of the reaction, the solvent used can be removed if necessary to obtain the propenyl group-containing compound (2). After the reaction, the propenyl group-containing compound (2) 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 mixture.

The heating temperature during the Claisen rearrangement reaction is preferably 150 to 220 ° C., more preferably 170 to 200 ° C., and even more preferably the rearrangement reaction in the presence of an inert gas such as nitrogen. When the heating temperature is equal to or higher than the above lower limit, the rearrangement reaction of the allyl group is likely to occur. When the heating temperature is not more than the above upper limit value, polymerization of the allyl group is unlikely to occur.

After the reaction, if necessary, the reaction product may be treated with water or the like.

The dropping time of the sodium hydroxide aqueous solution after the reaction is preferably 10 minutes to 30 minutes. If the dropping time is equal to or greater than the above lower limit, heat generation due to mixing can be suppressed and safe production can be performed. If the dropping time is equal to or less than the above upper limit value, the productivity is improved. The stirring time after dropping into the acid solution is preferably 15 to 60 minutes. If the stirring time is equal to or greater than the above lower limit, the neutralization reaction proceeds and the yield in the subsequent separation step is improved. If the stirring time is not more than the above upper limit value, the productivity is improved.

Examples of the method of converting the allyl group of the propenyl group-containing compound (2) into a 1-propenyl group include a method of dissolving the propenyl group-containing compound (2) in a solvent and heating it under the catalyst of the propenylation reaction.

The solvent used in the propenylation reaction may be any solvent that dissolves the propenyl group-containing compound (2), and a polar solvent is typically used.
Examples of the polar solvent include 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, and the like. Examples thereof include ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and tetrahydrofuran. As the solvent, one type may be used alone, or two or more types may be used in combination.

The solvent is preferably 20 to 900 parts by mass, particularly 50 to 600 parts by mass with respect to 100 parts by mass of the propenyl group-containing compound (2).

Examples of the catalyst for the propenylation reaction include alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononen, diazabicycloundecene and triethylamine, sodium tert-butoxide and potassium tert-butoxide. Examples thereof include lithium diisopropylamide, silicon-basic amine, lithium tetramethylpiperidin and the like. Of these, potassium hydroxide and sodium hydroxide are preferable because they are relatively inexpensive and side reactions are unlikely to occur. One type of catalyst may be used alone, or two or more types may be used in combination.

The amount of the catalyst used in the propenylation reaction is preferably 0.4 to 6.0 times by mole, more preferably 1.0 to 4.0 times by mole, based on the total molar amount of the hydroxyl groups of the propenyl group-containing compound (2). preferable. If the amount of the catalyst used is too small, the propenylation reaction will not proceed easily, and if the amount used is too large, excess alkali must be removed, resulting in a decrease in productivity.

The reaction temperature of the propenylation reaction is preferably 40 to 140 ° C, more preferably 70 to 120 ° C. When the reaction temperature is equal to or higher than the above lower limit, the propenylation reaction easily proceeds. When the reaction temperature is not more than the above upper limit value, polymerization of the propenyl group is unlikely 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.) and the like.

In the present invention, the propenyl group-containing compound (1) after the propenylation reaction and the propenyl group-containing compound (2) may be blended to obtain the propenyl group-containing composition of the present invention.

[Curable resin composition]
The curable resin composition of the present invention comprises the above-mentioned propenyl group-containing composition of the present invention, an epoxy resin, a maleimide resin, a phenol resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, and a radically polymerizable functional group. It contains one or more kinds of resins selected from the group consisting of a resin having a resin, an isocyanate resin, an acid anhydride resin, and a carbodiimide resin (hereinafter, these may be referred to as "curing components"), and the curing components include. , Preferably one or more resins selected from the group consisting of epoxy resins, maleimide resins and phenolic resins.

In the curable resin composition of the present invention, curing proceeds when the 1-propenyl group or allyl group of the propenyl group-containing composition of the present invention reacts with the maleimide group of the maleimide resin under predetermined conditions. .. As described above, in the present invention, the propenyl group-containing composition functions as a curing agent for the maleimide resin.
Further, in the case of an epoxy resin, the curing reaction proceeds by reacting the hydroxyl group of the propenyl group-containing composition of the present invention with the epoxy group of the epoxy resin. Again, the propenyl group-containing composition functions as a curing agent for the epoxy resin.
Moreover, the phenol resin can be used in combination with the epoxy resin.
The curable resin composition of the present invention has excellent adhesion to the cured product, and the curing reaction tends to proceed easily and the molecular weight of the cured product tends to increase. Therefore, particularly in the application of a semiconductor encapsulant, as a curing component. It preferably contains an epoxy resin.

In the curable resin composition of the present invention, the content ratio of the curing component is 0.01 to 1000 parts by mass with respect to 100 parts by mass of the propenyl group-containing composition of the present invention, and 0.1 to 500 parts by mass. It is preferably 1.0 to 300 parts by mass, more preferably 1.0 to 300 parts by mass. When the content ratio of the curing component is at least the above lower limit value, a cured product having excellent heat resistance and good adhesiveness can be obtained. If the content ratio of the curing component is not more than the above upper limit, a cured product that is uniform and has excellent curability can be produced.

<Curing component>
Hereinafter, each curing component contained in the curable resin composition of the present invention will be described.

<Maleimide resin>
The maleimide resin is a maleimide compound having an average of 1 or more maleimide groups in one molecule. Examples of the maleimide resin include bismaleimides having two maleimide groups in one molecule, polyphenylmethane maleimide, and the like.

Examples of bismaleimides include alkyl bismaleimide, diphenylmethane bismaleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide and the like. 4,4'-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4 , 4'-Diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are bonded via a methylene group.

As the maleimide resin, 4,4'-diphenylmethanebismaleimide and polyphenylmethanemaleimide are among the above-mentioned maleimide resins because of their excellent compatibility with the propenyl group-containing composition of the present invention and their relatively low cost. preferable.

As the maleimide resin, a commercially available product may be used. Examples of commercially available maleimide resins include product names "BMI-1100" (4,4'-diphenylmethanebismaleimide) and product names "BMI-2300" (polyphenylmethanemaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. ..

One type of maleimide resin may be used alone, or two or more types may be used in combination.

<Epoxy resin>
The epoxy resin is not particularly limited, and for example, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy. Resins, naphthol type epoxy resins, xylylene type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, stillben type epoxy resins, sulfur atom-containing epoxy resins, phosphorus atom-containing epoxy resins, etc. Be done.

As the epoxy resin, an epoxy resin in which at least a part of the hydroxyl groups of the propenyl group-containing composition is epoxidized may be used. The epoxidation of the hydroxyl group can be carried out by a known method. For example, by reacting a propenyl group-containing composition with epichlorohydrin, a part or all of the hydroxyl groups of the propenyl group-containing composition becomes -OZ (where Z is a glycidyl group). Epoxy resin can be obtained.

One type of epoxy resin may be used alone, or two or more types may be used in combination.

<Phenol resin>
Examples of the phenol resin include phenols such as phenol, cresol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and formaldehyde. , Benzaldehyde, salicylaldehyde, and other aldehyde group-containing compounds are condensed or co-condensed under an acidic catalyst to form a novolac-type phenolic resin; phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. Phenol-aralkyl resin synthesized from; aralkyl-type phenolic resins such as biphenylene-type phenol-aralkyl resin and naphthol-aralkyl resin; dicyclobenza synthesized by the copolymerization of phenols and / or naphthols with dicyclopentadiene. Dicyclopentadiene-type phenolic resins such as diene-type phenol novolac resin and dicyclopentadiene-type naphthol novolak resin; triphenylmethane-type phenol resin; terpen-modified phenol resin; paraxylylene and / or metaxylylene-modified phenol resin; melamine-modified phenol resin; cyclopentadiene. Modified phenolic resins; and phenolic resins obtained by copolymerizing two or more of these can be mentioned.

One type of phenol resin may be used alone, or two or more types may be used in combination.

<Benzooxazine resin>
Examples of the benzoxazine resin include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). Examples thereof include bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine). The benzoxazine resin may contain a structure in which the oxazine ring is ring-opened polymerized.
One type of benzoxazine resin may be used alone, or two or more types may be used in combination.

<Cyanate ester resin>
Examples of the cyanate ester resin include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4'. -Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) ) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol novolac Examples thereof include polyfunctional cyanate resins derived from cresol novolac and the like, and prepolymers in which these cyanate resins are partially triazined.

One type of cyanate ester resin may be used alone, or two or more types may be used in combination.

<Active ester resin>
The active ester resin is not particularly limited, but generally contains 2 ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Compounds having more than one are preferably used. The active ester resin is preferably one 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 preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin , Benzintriol, dicyclopentadiene type diphenol compound, phenol novolac and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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 product of phenol novolac, and an active ester resin containing a benzoylated product of phenol novolac are preferable. Of these, 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.

As the active ester resin, one type may be used alone, or two or more types may be used in combination.

<Resin having a radically polymerizable functional group>
Examples of the resin having a radically polymerizable functional group include a resin 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 an acrylic group, a methacryl group, a styryl group, an olefin group and a maleimide group. Preferred examples of the olefin group include an allyl group, a vinyl group and a propenyl group. Therefore, in one preferred embodiment, the radically polymerizable functional group is one or more selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an allyl group, a vinyl group, a propenyl group and a maleimide group.
The resin having a radically polymerizable functional group may have one kind or two or more kinds of radically polymerizable functional groups.

As the resin having a radically polymerizable functional group, one type may be used alone, or two or more types may be used in combination.

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

One type of isocyanate resin may be used alone, or two or more types may be used in combination.

<Acid anhydride resin>
Examples of the acid anhydride resin include resins having one or more acid anhydride groups in the molecule. Examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride anhydride. Trialkyltetrahydrophthalic anhydride, dodecenylhydride succinic acid, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, Pyromytz anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetra Carboxylide dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3- Examples thereof include dione, ethylene glycol bis (anhydrotrimeritate), and polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

One type of acid anhydride resin may be used alone, or two or more types may be used in combination.

<Carbodiimide resin>
Examples of the carbodiimide resin 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 the molecule. Specific examples of the carbodiimide resin include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

One type of carbodiimide resin may be used alone, or two or more types may be used in combination.

<Other ingredients>
The curable resin composition of the present invention may contain one or more other components in addition to the propenyl group-containing composition of the present invention and the above-mentioned curing components. Examples of other components include curing accelerators, inorganic fillers, solvents, mold release agents, surface treatment agents, colorants, thermoplastic polymers, organic fillers, flame retardants and the like.

Examples of the curing accelerator include other than the curing accelerator (hereinafter, also referred to as “curing accelerator (P)”) and the curing accelerator (P) that promote the curing reaction between the propenyl group-containing composition of the present invention and the maleimide resin. The curing accelerator (hereinafter, also referred to as “curing accelerator (Q)”) that promotes the curing reaction between the propenyl group-containing composition of the present invention and the epoxy resin can be mentioned.

Examples of the curing accelerator (P) include imidazoles and organic peroxides. When the curable resin composition contains an epoxy resin, if imidazoles are used as the curing accelerator (P), the curing reaction between the propenyl group-containing composition of the present invention and the epoxy resin is also promoted.

Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-unde__sylimidazole, 2-heptadecylimidazole, and 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 Examples thereof include imidazole and 1-cyanoethyl-2-phenylimidazole.

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

The curing accelerator (P) is preferably relatively stable at high temperature, has good solvent solubility, and is easy to handle. 2-Ethyl-4-methylimidazole is preferable for imidazoles, and 2-ethyl-4-methylimidazole is used for organic peroxides. The dialkyl peroxide dicumyl 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 a curing accelerator (P), the content thereof is preferably 0.1 to 5.0% by mass with respect 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.

Examples of the phosphorus compound include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, triphenyl phosphite and the like.
Examples of the tertiary amine include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7 and the like.

As the curing accelerator (Q), a phosphorus compound, particularly triphenylphosphine, is preferable because it has more excellent curability, heat resistance, electrical properties, and resistance to moisture resistance is less likely to decrease.

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 a curing accelerator (Q), the content thereof is preferably 0.1 to 5% by mass with respect to the epoxy resin.

Examples of the inorganic filler include crystalline silica powder, meltable silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder and the like. Of these, crystalline silica powder and melted silica powder are preferable. As the inorganic filler, one type may be used alone, or two or more types may be used in combination.

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 an epoxy resin in the solvent. The solvent is not particularly limited as long as it dissolves a propenyl group-containing composition, a curing component, or the like, and a polar solvent is typically used. Examples of the polar solvent include the same polar solvents as those mentioned in the description of the propenylation reaction. As the solvent, one type may be used alone, or two or more types may be used in combination.

The resin varnish contains the propenyl group-containing composition of the present invention, a curing component such as a maleimide resin and an epoxy resin, and a solvent as essential components. Using this resin varnish, for example, a copper-clad laminate as described later. Etc. 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 can be produced by mixing a curing component such as a maleimide resin or an epoxy resin, the propenyl group-containing composition of the present invention, other components blended as necessary, and a solvent. Mixing of each component can be carried out by a conventional method.

In the production of the resin varnish, even if the curing component such as maleimide resin, the propenyl group-containing composition of the present invention and the solvent are mixed, and then the maleimide resin or the like and the propenyl group-containing composition of the present invention are pre-reacted. good. By performing the prereaction in the varnish state, it is possible to suppress the precipitation of highly crystalline maleimide resin or the like from the resin varnish.

The reaction temperature at the time of carrying out the pre-reaction is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and even more preferably 80 to 120 ° C. If the reaction temperature is excessively low, the reaction will not proceed easily. If the reaction temperature is excessively high, it becomes difficult to control the reaction, and it becomes difficult to stably obtain a resin varnish.

Examples of the release agent include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents and the like.
Examples of the colorant include carbon black and the like.

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, and poly. Examples thereof include ether ether ketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin and the like.

Examples of the organic filler include a resin filler having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., an acrylic acid ester resin, a methacrylic acid ester resin, and a conjugated diene resin. A resin filler having a core-shell structure having a rubber-like core layer made of Can be mentioned.

Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, and red phosphorus; sulfamic acid. Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate, melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide.

The curable resin composition of the present invention is preferably cured by controlling the curing temperature to 150 to 250 ° C. As an example of the curing operation, there is a method of once curing at the above-mentioned suitable curing temperature for 30 seconds or more and 3 hours or less, and then further performing post-curing at the above-mentioned suitable curing temperature for 1 to 20 hours. ..

The propenyl group contained in the curable resin composition of the present invention, that is, the propenyl group contained in the propenyl group-containing compound (1) in the propenyl group-containing composition of the present invention is contained in the maleimide resin as compared with the allyl group. Easily reacts with maleimide groups. Therefore, the curable resin composition of the present invention has a high curing rate and is excellent in curability. Further, since the curable resin composition of the present invention has a high curing rate, it is not always necessary to use a curing accelerator that requires careful handling such as organic peroxides. By not blending the curing accelerator with the curable resin composition of the present invention, the handleability is improved.

The hydroxyl group contained in the curable resin composition of the present invention, that is, the hydroxyl group contained in the propenyl group-containing compound (1) in the propenyl group-containing composition of the present invention reacts with the epoxy group contained in the epoxy resin. The reaction rate between the hydroxyl group and the epoxy group can be accelerated by the presence of a curing accelerator such as triphenylphosphine. When cured with an epoxy resin, the propenyl group of the propenyl group-containing compound (1) undergoes a self-polymerization reaction, and the crosslinked structure generated by the self-polymerization has hydrophobicity and flexibility, so that the water absorption of the cured product is reduced. Adhesive strength is improved.

Curing of a curable resin composition containing a maleimide resin is usually heated at a high temperature of 80 to 250 ° C. Therefore, in the conventional curable resin composition, a part of the resin component volatilizes during curing and voids are generated in the cured product. There was something. However, since the curable resin composition of the present invention uses the propenyl group-containing composition of the present invention, the curing reaction is fast, so that it is difficult to volatilize during curing. Therefore, voids are less likely to occur in the cured product, and the defect rate is low in the manufacture of electronic parts and the like, so that the productivity is high. Further, by using the propenyl group-containing composition of the present invention, a highly hydrophobic crosslinked structure is generated, the water absorption of the cured product is lowered, and when an electronic component or the like using the cured product is allowed to act at a high temperature, etc. However, cracks are unlikely to occur.

The curable resin composition of the present invention containing the propenyl group-containing composition of the present invention has a high density of propenyl groups per unit weight of the propenyl group-containing compound (1), and the crosslinked structure at the time of curing becomes high density. Therefore, the cured product has excellent heat resistance.
As described above, by using the curable resin composition of the present invention, a cured product having excellent heat resistance and low water absorption can be formed in a short time while suppressing the formation of voids, such as a laminated board and a sealing material. Can be manufactured with high productivity.

The use of the curable resin composition of the present invention will be further described later. Examples include 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 curing for these uses, or may be cured and used in a manufacturing process applied to these uses.

[Cured product]
By curing the curable resin composition of the present invention, the cured product of the present invention can be obtained. The cured product of the present invention obtained by curing the curable resin composition of the present invention has excellent properties in curability, crack resistance, heat resistance, low water absorption, adhesiveness, low linear expansion, moldability, and strength. It has.

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. At the time of the thermosetting reaction, it is preferable to appropriately select the curing temperature according to the type of the curing component used. For example, when a maleimide resin is used, the curing temperature is usually 80 to 250 ° C., and when an epoxy resin is used, it is usually 100 to 200 ° C. It is also possible to lower the curing temperature by adding a curing accelerator to these curing components. The curing reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and even more preferably 3 to 15 hours. When the reaction time is at least the above lower limit value, the curing reaction tends to proceed sufficiently, which is preferable. On the other hand, when the reaction time is not more than the above upper limit value, deterioration due to heating and energy loss during heating can be easily reduced, which is preferable.

[Use]
The curable resin composition of the present invention has excellent curability, and the cured product using the curable resin composition of the present invention has crack resistance, heat resistance, low water absorption, adhesiveness, toughness, and low linear expansion property. Excellent moldability.

Therefore, the propenyl group-containing composition, 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, paint fields such as optical materials, paints for automobiles such as electrodeposition paints for automobiles, heavy-duty anticorrosion paints for ships and bridges, paints for inner surface coating of beverage cans; composite materials, laminates, semiconductor encapsulants, liquid insulation. Electrical and electronic fields such as encapsulants, insulating powder paints, coil impregnation, etc .; Seismic reinforcement of bridges, concrete reinforcement, flooring of buildings, lining of water supply facilities, drainage / water permeable pavement, adhesives for structures / vehicles / aircraft It can be suitably used for all applications such as civil engineering, construction, and adhesives. Of these, it is particularly useful for electrical and electronic components.

[Laminated board]
As a method for producing a laminated board using the curable resin composition of the present invention, a laminate containing a prepreg in which a fibrous base material is impregnated with the above-mentioned resin varnish made of the curable resin composition of the present invention is heated and pressed. A method of producing a laminated board by curing the laminated board can be mentioned.

More specifically, the fibrous base material is impregnated with a resin varnish and dried to remove the solvent to obtain a prepreg. This prepreg and other base materials to be used as needed are laminated to form a laminate, and the laminate is heated and pressed to be cured to obtain a laminate.

The number of laminated prepregs in the laminate may be one layer or two or more layers. In the laminate, a base material other than the prepreg may be laminated. Examples of other base materials include metal foils such as copper foils.

Examples of the fibers constituting the fibrous base material include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers and stainless fibers; natural fibers such as cotton, linen and paper; and synthetic organic fibers such as polyester resin and polyamide resin. Can be 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 short fibers, yarns, mats, and sheets.

The amount of the resin varnish to be impregnated in the fibrous base material 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). To do so.
The heating temperature at the time of heating and pressurizing the laminate is preferably the above-mentioned curing temperature. The pressurizing condition is preferably ^{2 to 20 kN / m 2.}

The laminated board produced in this manner includes a fiber-reinforced resin layer containing a fibrous base material and a cured product of a resin varnish. The number of fiber-reinforced resin layers included in the laminated board may be one layer or two or more layers. As described above, the laminated board may have a metal foil layer such as copper foil.

[Encapsulant]
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, and is adopted, for example, in known semiconductors and the like. A shape similar to the shape can be adopted.
Examples of the method for forming the encapsulant using the curable resin composition of the present invention include a method for encapsulating a semiconductor by using a transfer molding method, a compression molding method, or the like.

Hereinafter, the content of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination of the values of Examples.

[Material used]
The compounds and resins used in the following examples and comparative examples are as follows.

-Other propenyl resins: Propenyl compounds of phenol biphenylene resins represented by the following structural formula ("BPN-01S" manufactured by Gun Ei Chemical Industry Co., Ltd.)

-Maleimide resin: Polyphenylmethane maleimide represented by the following structural formula ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd.)

-Phenol resin: Phenol novolac represented by the following structural formula ("PSM4261" manufactured by Gun Ei Chemical Industry Co., Ltd.)

-Epoxy resin: Tetramethylbiphenyl type epoxy resin represented by the following structural formula ("YX4000" manufactured by Mitsubishi Chemical Corporation)

・ Curing accelerator: Triphenylphosphine

[Example 1: Production of propenyl group-containing composition]
<Allylation>
To a 10 L autoclave, 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, sealed, and heated to 40 ° C. The temperature was raised to 65 ° C. over 1 hour. After aging at 65 ° C. for 5 hours, the mixture was cooled to room temperature and the autoclave was opened. To this, 1678 g of water and 1600 g of methyl isobutyl ketone were added to dissolve the inorganic salt and crystals, and the aqueous layer was removed by a liquid separation operation. 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, the methyl isobutyl ketone was distilled off, and the compound represented by the following formula (A) (hereinafter, "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 mass% sodium hydroxide aqueous solution were placed in a 2 L separable flask and cooled to 10 ° C., the above N, N-diethylaniline solution was added dropwise, and the mixture was stirred for 30 minutes. After that, it was allowed to stand, and the upper layer and the lower layer were extracted respectively. 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 then 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. As a gray solid, a compound represented by the following formula (2-1), which is a propenyl group-containing compound (2) (hereinafter, "Compound (2-1)". ) ”) Was obtained in an amount of 148 g (1.19 mol, 2-step yield 80.4%).

<Propenylization>
100 parts by mass of compound (2-1) 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%) was 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. Next, 203 parts by mass of methyl isobutyl ketone was added, neutralized with sulfuric acid, and then washed with water was repeated. Next, by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure at 120 ° C., a compound having a structure represented by the following formula (1-1), which is a propenyl group-containing compound (1) (hereinafter, “Compound (1)” -1) ”) was obtained in an amount of 95 parts by mass of a propenyl group-containing composition.

As is clear from the following composition analysis, this propenyl group-containing composition includes a compound (1-1) and a compound represented by the following formula (2-1) (hereinafter, "compound (2-1)". It is referred to as.).

The composition of the obtained propenyl group-containing composition was analyzed by the following method. In addition, the melt viscosity and softening point were measured by the following methods. The results are shown in Table 1.

<Composition analysis of propenyl group-containing composition>
The propenyl group-containing composition was dissolved in an amount of 1% by mass based on acetone, and analyzed by liquid chromatography under the following conditions.
Equipment: Agent1100 Series Column: Imtakat United UK-C18
(4.6 mm ID x 25 cm L x 3 μm)
Column tank temperature: 40 ° C
UV detection wavelength: 280 nm
Mobile phase condition: pure water / methanol = 25/75

<Measurement of melt viscosity of propenyl group-containing composition>
The propenyl group-containing composition was melted on a hot plate of a cone plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150 ° C., and the melt viscosity was measured at a rotation speed of 750 rpm.

<Measurement of softening point of propenyl group-containing composition>
The softening point of the propenyl group-containing composition was measured according to JIS K7234.

[Example 2: Production of propenyl group-containing composition]
In Example 1, the same procedure was carried out except that the sulfuric acid used for neutralization in <propenylation> was changed to hydrochloric acid. The results are shown in Table 1.

[Example 3: Production of propenyl group-containing composition]
In Example 1, 100 parts by mass of methanol used in <propenylation> was changed to 900 parts by mass of dimethyl sulfoxide, and 79 parts by mass of potassium hydroxide was changed to 337 parts by mass of t-butoxypotassium. The results are shown in Table 1.

[Comparative Example 1: Production of Propenyl Group-Containing Composition]
In Example 1, the same procedure was carried out except that the temperature at the time of heating and depressurizing in <propenylation> was set to 150 ° C. The results are shown in Table 1.

[Example 4: Production of propenyl group-containing composition]
In Example 1, 100 parts by mass of compound (2-1) was changed to 100 parts by mass of compound (2-2) (DABPA of Daiwa Kasei Kogyo Co., Ltd.) in <propenylation>, but the same procedure was carried out. The results are shown in Table 2.
As is clear from the following composition analysis, the propenyl group-containing composition obtained in Example 4 is a compound represented by the following formula (1-2) (hereinafter, referred to as "compound (1-2)". " ) And a compound represented by the following formula (2-2) (hereinafter, referred to as “compound (2-2)”).

[Example 5]
After mixing the propenyl group-containing composition produced in Example 1 at the ratio shown in Table 3 with a maleimide resin to obtain a curable resin composition, a curing reaction was carried out at 120 ° C. for 2 hours and then at 200 ° C. for 6 hours. Was carried out to prepare a cured product.
Tg (tan δ) and storage elastic moduli E'(250 ° C.) and E'(40 ° C.) were measured on the obtained cured product by the method shown below. Moreover, the shear adhesive strength to the metal (Cu) was measured using the produced curable resin composition. The results are shown in Table 3.

[Example 6]
After mixing the propenyl group-containing composition produced in Example 4 at the ratio shown in Table 3 with a maleimide resin to obtain a curable resin composition, a curing reaction was carried out at 120 ° C. for 2 hours and then at 200 ° C. for 6 hours. Was carried out to prepare a cured product.
Tg (tan δ) and storage elastic moduli E'(250 ° C.) and E'(40 ° C.) were measured on the obtained cured product by the method shown below. Moreover, the shear adhesive strength to the metal (Cu) was measured using the produced curable resin composition. The results are shown in Table 3.

[Comparative Example 2]
After mixing other propenyl resin and maleimide resin at the ratio shown in Table 3 to obtain a curable resin composition, a curing reaction was carried out at 120 ° C. for 2 hours and then at 200 ° C. for 6 hours to obtain a cured product. Made.
Tg (tan δ) and storage elastic moduli E'(250 ° C.) and E'(40 ° C.) were measured on the obtained cured product by the method shown below. Moreover, the shear adhesive strength to the metal (Cu) was measured using the produced curable resin composition. The results are shown in Table 3.

<Cured product: Tg (tan δ) and storage elastic modulus E'(250 ° C), E'(40 ° C)>
Dynamic viscoelasticity measurement (DMA: Dynamic) using a test piece obtained by cutting a cured product to a length of 5 cm, a width of 1 cm, and a thickness of 4 mm under the following conditions.
Mechanical Analysis) was performed, and Tg (tan δ) and storage elastic modulus (E') at 250 ° C. and 40 ° C. were measured.
Analyzer: EXSTAR6100 manufactured by Seiko Instruments Inc.
Measurement mode: 3-point bending mode Measurement temperature range: 30 ° C to 280 ° C
Temperature rise rate: 5 ° C / min
Temperature drop rate: 5 ° C / min
* The temperature at the peak top of tan δ was defined as Tg (tan δ).

<Shear adhesion strength to metal>
It was carried out in accordance with JIS-K6850. That is, the curable resin composition is 25 mm wide x 12.5 mm long between two metal pieces (copper plate (double-sided sandblasted plate manufactured by Yutaka Panel Service Co., Ltd.)) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm. It was applied so as to become. After coating, it was put into a constant temperature bath and cured at 120 ° C. for 2 hours and 175 ° C. for 6 hours to prepare a peeling test piece.
The prepared peeling test piece was subjected to a tensile shear test using a tensile tester "Instron 5582" (manufactured by Instron) at a speed of 5 mm / min with a test number of n = 3, and the tensile shear strength was measured and averaged. The value was calculated.

[Example 7, Comparative Examples 3 and 4]
With the formulation shown in Table 4, the propenyl group-containing composition produced in Example 1, other propenyl resin, or phenol resin was mixed with an epoxy resin and a curing accelerator to obtain a curable resin composition, and then 120. A curing reaction was carried out at ° C. for 2 hours and then at 200 ° C. for 6 hours to prepare a cured product. The storage elastic modulus E'(250 ° C.) of the obtained cured product was measured by the method shown above. Further, using the obtained curable resin composition, an aluminum plate (double-sided sandblasting plate manufactured by Yutaka Panel Service Co., Ltd.) is used instead of the copper plate (double-sided sandblasting plate manufactured by Yutaka Panel Service Co., Ltd.), and the metal (double-sided sandblasting plate manufactured by Yutaka Panel Service Co., Ltd.) is used in the same manner as above. The shear bond strength with respect to aluminum) was measured. Further, the obtained cured product was subjected to a water absorption test by the method shown below.
These results are shown in Table 4.
In Comparative Example 3, the cured product was brittle in the E'(250 ° C.) and water absorption tests, and the viscosity was high in the shear adhesive strength test, so that a test piece could not be prepared and evaluation could not be performed.

<Water absorption test>
A test piece obtained by cutting the cured product to a length of 2 cm, a width of 2 cm, and a thickness of 4 mm was prepared, and the atmosphere was 85 ° C./85% RH in a constant temperature and humidity device (Nagano Science Co., Ltd. "LH21-11P"). After leaving it for 168 hours underneath, the water absorption rate of the cured product was calculated from the mass of the test piece before and after water absorption by the following formula.
Water absorption rate (%) = {(mass of test piece after water supply-mass of test piece before water supply) / (mass of test piece before water supply)} x 100

[Example 8, Comparative Example 5]
After mixing the propenyl group-containing composition or compound (2-1), maleimide resin, epoxy resin and curing accelerator produced in Example 1 with the formulation shown in Table 5 to obtain a curable resin composition, A cured product was prepared by carrying out a curing reaction at 200 ° C. for 6 hours.
With respect to the obtained cured product, the storage elastic modulus E'(40 ° C.), the storage elastic modulus E'(250 ° C.), and Tg (tan δ) were measured by the methods shown above. In addition, the coefficient of linear expansion and the weight loss at 200 ° C. were evaluated by the methods shown below.
Further, using the obtained curable resin composition, a copper plate (double-sided sandblasted plate manufactured by Yutaka Panel Service Co., Ltd.) and an aluminum plate (double-sided sandblasted plate manufactured by Yutaka Panel Service Co., Ltd.) are used in the same manner as described above. The shear bond strength with respect to aluminum) was measured, and the shear bond strength was evaluated according to the following criteria.
◯: Shear adhesive strength of 8.0 MPa or more ×: Shear adhesive strength of less than 8.0 MPa Further, gel time evaluation was carried out by the method shown below.
These results are shown in Table 5.
In Comparative Example 5, the cured product was brittle in the tests of the storage elastic modulus E'(40 ° C.), the storage elastic modulus E'(250 ° C.), and Tg (tan δ), and the test piece could not be prepared and the evaluation could not be performed. rice field.

<Evaluation of coefficient of linear expansion>
The cured product was cut into a columnar test piece with a diameter of about 7 mm and a thickness of 4 mm, and thermomechanical analysis was performed in compression mode using a thermomechanical analyzer (TMA: EXSTAR6000 manufactured by Seiko Instruments Inc.) (measurement weight: 30 mN, heating rate: twice at 5 ° C / min, measurement temperature range: 30 ° C to 3000 ° C). From the results of the second measurement, the coefficient of linear expansion in the temperature range shown in Table 5 was determined.

<Evaluation of weight loss at 200 ° C>
The cured product was cut into rectangular parallelepiped test pieces having a length of 4 cm, a width of 2 cm, and a thickness of 4 mm, placed in a heating furnace (Perfect oven: SPHH-202 manufactured by ESPEC), and stored at an isothermal temperature at 200 ° C. The weight change rate was calculated from the weight of the cured product before heating and the weight of the cured product during the test time shown in Table 5.
Weight change rate (%) =-{(mass of test piece after weight change-mass of test piece before weight change) / (mass of test piece before weight change)} x 100

<Gel time evaluation>
0.1 g of the curable resin composition was placed on a gel time tester (BIG HEART, manufactured by Imoto Seisakusho Co., Ltd.) heated to 175 ° C., and the time until gelation proceeded (gel time) was measured. The time until gelation proceeded was defined as the time during which the curable resin composition lost its fluidity as a liquid at 175 ° C.

[Evaluation of results]
From Table 3, the cured products of Examples 5 and 6 using the propenyl group-containing composition of Example 1 are superior in heat resistance and elastic modulus as compared with the cured products of Comparative Example 2 using other propenyl resins. It can be seen that the change in rate is small and that it exhibits high adhesiveness to metals.
From Table 4, the cured product of Example 7 using the propenyl group-containing composition of Example 1 has a lower elastic modulus at a higher temperature than the cured product of Comparative Examples 3 and 4 using other propenyl resins and phenol resins. It is a rate, and it can be seen that it exhibits low hygroscopicity and high adhesiveness.
From Table 5, the cured product of Example 8 using the propenyl group-containing composition of Example 1 has a smaller coefficient of linear expansion and strength than the cured product of Comparative Example 5 using the compound (2-1). It can be seen that the adhesive strength and heat-decomposability are high, the gel time is short, and the moldability is excellent.

Claims (8)

A propenyl group-containing composition containing a compound represented by the following formula (1), wherein the content of the compound represented by the formula (1) is 80.0 to 99.9% by mass. Composition.

(In the above formula (1), X is a direct bond, -SO _2- , -O-, -CO-, -C (CF ₃ ) _2- , -S- and an aliphatic hydrocarbon having 1 to 20 carbon atoms. It is a divalent linking group selected from the groups. R ¹ and R ² are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms or halogen atoms, and may be the same or different from each other.) The propenyl group-containing composition according to claim 1, which contains 0.1 to 20.0% by mass of a compound represented by the following formula (2).

(In the above formula (2), X, R ¹ , and R ² are synonymous with those in the above formula (1).) The propenyl group-containing composition according to claim 1 or 2, wherein the proportion of the trans compound in which both of the two propenyl groups are of the trans type among the compounds represented by the formula (1) is 20 to 95%. The propenyl group-containing composition according to any one of claims 1 to 3, wherein the proportion of the cis form in which the two propenyl groups are both cis type among the compounds represented by the formula (1) is 30% or less. thing. The propenyl group-containing composition according to any one of claims 1 to 4, wherein the melt viscosity at 150 ° C. is in the range of 0.01 to 10.0 P. An epoxy resin, a maleimide resin, a phenol resin, a benzoxazine resin, a cyanate ester resin, an active ester resin, and a radically polymerizable functional group are added to 100 parts by mass of the propenyl group-containing composition according to any one of claims 1 to 5. A curable resin composition containing 0.01 to 1000 parts by mass of at least one selected from the group consisting of a resin having a resin, an isocyanate resin, an acid anhydride resin and a carbodiimide resin. A cured product obtained by curing the curable resin composition according to claim 6. An electrical / electronic component containing a cured product of the curable resin composition according to claim 6.