WO2020017141A1 - Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound and method for producing compound - Google Patents

Abstract

A reactive diluent which contains a compound represented by general formula (1). (In formula (1), n represents 0 or 1.)

Description

Reactive diluent, composition, encapsulant, cured product, substrate, electronic component, epoxy compound, and method for producing compound

The present invention relates to a reactive diluent, a composition, a sealing material, a cured product, a substrate, an electronic component, an epoxy compound, an intermediate in the production of the epoxy compound, a method for producing the intermediate, and a method for producing the epoxy compound. .
This application claims priority based on Japanese Patent Application No. 2018-134435 and Japanese Patent Application No. 2018-134436 for which it applied to Japan on July 17, 2018, and uses the content here.

Epoxy resin compositions have excellent electrical performance and adhesive strength, and are widely used as interlayer insulating materials for printed circuit boards of electrical and electronic equipment, sealing materials, matrix materials for various structural members, adhesives, etc. I have.
In particular, current electronic devices are required to be able to transmit and receive high-speed and large-volume information. However, as wiring becomes finer due to the miniaturization of equipment, the delay between transmissions of electric signals increases due to the large inter-wiring capacity of the conventional interlayer insulating material, and the transmission and reception of high-speed and large-capacity information is performed. Was hindered.
Since the delay time is proportional to the capacitance between the wirings, if the capacitance between the wirings is reduced by lowering the dielectric of the interlayer insulating material, the speed of transmission of the electric signal can be increased.

Two characteristics, dielectric loss tangent and relative dielectric constant, are important as dielectric characteristics. As a method of lowering the dielectric constant of an epoxy resin, a method of increasing the amount of silica filler is known. However, when the amount of the silica filler is increased, the dielectric loss tangent can be reduced, but there is a problem that the dielectric constant increases.

Epoxy resin compositions are widely used in various applications because of their excellent adhesiveness and electromechanical properties. Epoxy resin compositions are usually provided with preferable characteristics according to the use by adding various additives. For example, when an epoxy resin composition is used as a semiconductor encapsulant, with the recent miniaturization of electronic devices, it is necessary to fill the encapsulant into minute gaps. It has been demanded. As a means for reducing the viscosity of a high-viscosity resin composition, a diluent is used. Diluents are divided into non-reactive and reactive. Since the reactive diluent reacts with the resin component of the resin composition and cures together with the resin composition to become a part of a cured product, there is an advantage that the diluent component hardly bleeds out.
As a reactive diluent for lowering the viscosity of the resin composition and exhibiting excellent dielectric properties, for example, a compound in which a glycidyl group is bonded to an isostearic acid raw material via an ester bond as described in Non-Patent Document 1 ( (Product name: FOLDI) is disclosed.

(4) When the epoxy resin composition is used as a cured product, the cured product becomes rigid due to its high modulus of elasticity, and thermal expansion and curing shrinkage occur to easily apply stress to peripheral members. As a result, a dimensional deviation or a crack may cause a malfunction. For this reason, a material that is flexible when cured is required.

The present invention has been made to solve the above-described problems, and has realized a reduction in the viscosity of a resin composition, and a cured product of the resin composition has realized low dielectric properties and flexibility. It is an object of the present invention to provide a novel reactive diluent capable of satisfying the above requirement.
Another object of the present invention is to provide a composition containing the reactive diluent.
Another object of the present invention is to provide a sealing material containing the composition.
Another object of the present invention is to provide a cured product of the composition.
Another object of the present invention is to provide a substrate including the cured product.
Another object of the present invention is to provide an electronic component including the cured product.
Further, the present invention provides a novel epoxy compound which realizes a low viscosity of a resin composition and achieves a low dielectric property and imparts flexibility in a cured product of the resin composition. Aim.
Another object of the present invention is to provide an intermediate in the production of the epoxy compound.
Another object of the present invention is to provide a method for producing the intermediate.
Another object of the present invention is to provide a method for producing the epoxy compound.

[1] a reactive diluent containing the following component A,
Component A: a compound represented by the following general formula (1).

(In the formula (1), n is 0 or 1.)
[2] a composition comprising the following components A and B,
Component A: a compound represented by the following general formula (1),

(In the formula (1), n is 0 or 1.)
Component B: a compound having two or more groups containing an epoxy ring in the molecule.
[3] The composition according to [2], further comprising the following component C:
Component C: curing agent.
[4] The composition according to [3], further comprising the following component D:
Component D: curing accelerator.
[5] A sealing material containing the composition according to [3] or [4].
[6] A cured product of the composition according to [3] or [4].
[7] A substrate comprising the cured product according to [6].
[8] An electronic component comprising the cured product according to [6].
[9] A compound represented by the following general formula (1).

(In the formula (1), n is 0 or 1.)
[10] A compound represented by the following general formula (2).

(In the formula (2), n is 0 or 1.)
[11] A method for producing a compound represented by the following general formula (2), comprising obtaining a compound represented by the following general formula (2) by hydroxylating a compound represented by the following general formula (3): .

(In the formula (3), n is 0 or 1.)

(In the formula (2), n is 0 or 1.)
[12] A method for producing a compound represented by the following general formula (1), comprising epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1): .

(In the formula (2), n is 0 or 1.)

(In the formula (1), n is 0 or 1.)

ADVANTAGE OF THE INVENTION According to this invention, the low viscosity of a resin composition is implement | achieved, and in the hardened | cured material of this resin composition, realization of a low dielectric property and provision of flexibility can provide a novel reactive diluent. .
Further, according to the present invention, a composition containing the reactive diluent can be provided.
Further, according to the present invention, a sealing material containing the composition can be provided.
Further, according to the present invention, a cured product of the composition can be provided.
Further, according to the present invention, a substrate provided with the cured product can be provided.
Further, according to the present invention, an electronic component including the cured product can be provided.
Further, according to the present invention, it is possible to provide a novel epoxy compound that realizes a low viscosity of a resin composition and achieves a low dielectric property and imparts flexibility in a cured product of the resin composition. .
Further, according to the present invention, an intermediate in the production of the epoxy compound can be provided.
Further, according to the present invention, a method for producing the intermediate can be provided.
Further, according to the present invention, a method for producing the epoxy compound can be provided.

Hereinafter, embodiments of the present invention will be described.

{Compound (1)}
The compound according to the embodiment of the present invention is a compound represented by the following general formula (1) (may be abbreviated as “compound (1)”).

(In the formula (1), n is 0 or 1.)

According to the compound (1), when compounded into a resin composition, the viscosity of the resin composition is reduced, and the cured product of the resin composition achieves low dielectric properties and imparts flexibility. Achievable.
Compound (1) has a structure of a saturated hydrocarbon in the molecule. Therefore, when it is blended with the resin composition, it is considered that the cured product contributes to exhibiting low dielectric properties.
Compound (1) has a branched saturated hydrocarbon structure in the molecule. Therefore, it is considered that when it is mixed with the resin composition, it contributes to lowering the viscosity of the resin composition. In addition, it is considered that this structure contributes to imparting flexibility to the cured product when blended with the resin composition.

In the present specification, "providing flexibility" refers to a comparison between a resin composition containing the compound according to the present invention and a resin composition not containing the compound according to the present invention. This means that the resin composition containing such a compound is more easily deformed and hardly broken.

化合物 Compound (1) can be colorless and transparent. Therefore, when compound (1) is blended with the resin composition, compound (1) is also prevented from causing coloring of the resin composition.

{Compound (2)}
The compound according to the embodiment of the present invention is a compound represented by the following general formula (2) (sometimes abbreviated as “compound (2)”).

(In the formula (2), n is 0 or 1.)

Compound (2) can be used as an intermediate in the production of compound (1).

<< Method for producing compound (1) / method for producing compound (2) >>
Compound (1) can be produced, for example, by the following method. Compound (1) is not limited to those produced by the following method.

Compound (1) can be produced by subjecting a compound represented by the following general formula (3) (may be abbreviated as “compound (3)”) to epoxidation after hydroxylation.
In this specification, “epoxidation” means to introduce an epoxy ring or a group containing an epoxy ring, unless otherwise specified.

(In the formula (3), n is 0 or 1.)

The method for producing the compound (1) may include the following steps 1 and 2.
Step 1: a step of hydroxylating compound (3) to obtain compound (2).
Step 2: a step of epoxidizing the compound (2) obtained in the above step 1 to obtain a compound (1).

<Step 1>
The method for producing compound (1) of the embodiment includes a step (step 1) of hydroxylating compound (3) to obtain compound (2).
That is, the present invention provides a method for producing a compound (2), which comprises obtaining a compound (2) by hydroxylating the compound (3).
The method for producing the compound (1) of the embodiment may include a step of obtaining the compound (2) by hydroborating the compound (3) and then hydroxylating the compound (3).

The step 1 includes:
The step of reacting the compound (3) with a hydroborating agent to form a hydroboron, followed by reacting with a peroxide to oxidize and hydroxylate to obtain the compound (2) may be performed.

(In the formula, n is 0 or 1.)

As the hydroborating agent, a substance which reacts with an alkene to cause a hydroboration reaction can be used, and may be selected from various substances capable of hydroboration. Examples of the hydroborating agent include compounds having a BH bond in the molecule, and examples thereof include borane, borane derivatives, and complexes thereof. Examples of the borane derivative include a monoalkyl borane, a dialkyl borane and a compound represented by the following general formula (3a). From the viewpoint of yield and selectivity, 9-borabicyclo [3.3.1] nonane (9 —BBN) or NH ₃ BH ₃ [in the compound represented by the following general formula (3a), R ¹ to R ⁶ are hydrogen atoms]. Examples of the complex include a tetrahydrofuran (THF) complex, a dimethylsulfide complex, and the like, and from the viewpoint of yield and selectivity, a 9-BBN.THF complex or an NH ₃ BH ₃ .THF complex is preferable.

(In the formula, R ¹ to R ⁶ are each independently a hydrogen atom or an alkyl group.)
The alkyl group of R ¹ to R ⁶ may be a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Etc. can be exemplified.
Commercially available NH ₃ BH ₃ may be used, and a step of synthesizing NH ₃ BH ₃ may be provided prior to step 1.

Compound (3) can be obtained by multiplying isobutylene.
The compound (3) has an isomer that is a compound represented by the following general formula (3 ′) (may be abbreviated as “compound (3 ′)”). As shown in the above, the compound (3) reacts more than the compound (3 ′), and the hydroxylation proceeds.
Therefore, the method for producing the compound (1) of the embodiment includes a step (step 1) of obtaining a compound (2) by hydroborating a raw material containing the compound (3) and the compound (3 ′) and then hydroxylating the raw material. May be something. Even if the raw material contains the compound (3 ′), the compound (3 ′) does not participate in the above reaction and can be removed after the reaction.

(In the formula (3 ′), m is 0 or 1.)

The amount of the hydroborating agent to be used may be appropriately adjusted according to the type of the compound in the reaction system, and the amount of the BH bond is 0.9 to 3 based on 1 equivalent of the carbon-carbon unsaturated bond to be reacted. It is preferably in the range of equivalents, more preferably in the range of 1 to 3 equivalents, and even more preferably in the range of 1.1 to 1.5 equivalents. When it is at least the lower limit, the yield will be better, and when it is at most the upper limit, purification will tend to be better.

The temperature (reaction temperature) of the reaction for hydroboration may be appropriately adjusted according to the type of the compound in the reaction system, but is preferably in the range of -80 to 120 ° C, for example, preferably in the range of -80 to 80 ° C. The temperature is preferably in the range of -30 ° C, more preferably in the range of -30 to 50 ° C, and even more preferably in the range of -30 to 40 ° C. Alternatively, it is preferably in the range of −80 to 120 ° C., more preferably in the range of 0 to 100 ° C., and even more preferably in the range of 50 to 90 ° C.
When it is at least the lower limit, the reaction rate is good and the reaction efficiency is good, and when it is at most the upper limit, the risk of decomposition of the raw materials and products tends to be reduced.

時間 The time (reaction time) of the reaction for hydroboration may be appropriately adjusted according to other conditions such as the reaction temperature, and may be, for example, 0.5 to 100 hours.

Examples of the peroxide include hydrogen peroxide, perbenzoic acid, benzoyl peroxide and the like, and hydrogen peroxide is preferable.
Commercially available hydrogen peroxide can be used. The amount of hydrogen peroxide to be used is not particularly limited, but is preferably in the range of 1 to 5 equivalents to 1 equivalent of the carbon-carbon unsaturated bond subjected to the reaction with the hydroborating agent, and preferably 1 to 2 equivalents. More preferably, it is within the range. When the amount is equal to or more than the lower limit, the reaction can proceed efficiently, and when the amount is equal to or less than the above upper limit, there is a tendency that a possibility that a side reaction such as oxidation of the generated hydroxy compound proceeds and the yield is reduced is reduced.

The oxidation in step 1 can be performed under basic conditions. The basic condition includes a condition in which a peroxide is used in combination with a base, and includes a solution in which a peroxide and a base are added.
Examples of the base include inorganic bases. Examples of the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, and carbonate. Calcium, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate and the like can be mentioned. Among these, sodium hydroxide, potassium hydroxide, or lithium hydroxide is preferred from the viewpoint of reaction yield, reaction temperature, simplicity of operation, economy, and the like.

The temperature of the hydroxylation reaction (reaction temperature) may be appropriately adjusted depending on the type of the compound in the reaction system, but is preferably in the range of -80 to 80 ° C, for example, -30 to 50 ° C. Is more preferably in the range of −30 to 40 ° C. When it is not less than the above lower limit, the reaction rate is good and the reaction efficiency is good, and when it is not more than the above upper limit, the risk of decomposition of the raw materials and products is small.

The reaction time for the hydroxylation (reaction time) may be appropriately adjusted depending on other conditions such as the reaction temperature, and may be, for example, 0.5 to 100 hours.

反 応 The reaction of the above step 1 may be performed in the presence of a solvent. One type of solvent may be used alone, or two or more types may be used in combination. The solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, dimethyl sulfide, and trimethylamine. From above, diethyl ether, tetrahydrofuran, dimethyl sulfide, and trimethylamine are preferred, and diethyl ether and tetrahydrofuran are more preferred.

<Step 2>
The method for producing compound (1) of the embodiment includes a step (step 2) of obtaining compound (1) by epoxidizing compound (2) obtained in step 1 above.
The method for producing the compound (1) of the embodiment includes a step of epoxidizing the compound (2) obtained in the step 1 and introducing an epoxy ring or a group containing an epoxy ring to obtain the compound (1). May be something.
The method for producing the compound (1) of the embodiment may include a step of glycidylating the compound (2) obtained in the above step 1 and introducing a glycidyl group to obtain the compound (1).

The step 2 includes:
The step of reacting the compound (2) with epihalohydrin to perform epoxidation (glycidylation) to obtain the compound (1) may be performed.

(In the formula, n is 0 or 1.)

Epihalohydrin includes epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. Epihalohydrin may be a compound represented by the following general formula (4) (sometimes abbreviated as “compound (4)”). These may be used alone or in combination of two or more.

(In the formula (4), X represents a halogen atom.)

Examples of the halogen atom include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

Among them, epichlorohydrin is preferred as epihalohydrin because of its easy industrial availability.

The amount of epihalohydrin used may be appropriately adjusted according to the type of the compound in the reaction system. For example, epihalohydrin may be added in the range of 2 to 10 equivalents to 1 equivalent of the hydroxyl group in compound (2). No.

The epoxidation reaction can be performed under basic conditions. The basic conditions include in a liquid to which a basic catalyst has been added.
Examples of the basic catalyst include an alkaline earth metal hydroxide, an alkali metal carbonate, and an alkali metal hydroxide. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent epoxidation catalytic activity, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid.

The amount of the basic catalyst to be used may be appropriately adjusted according to the type of the compound in the reaction system and the like. For example, 0.9 to 2 equivalents of the basic catalyst are added to 1 equivalent of the hydroxyl group in the compound (2). Are added at once or gradually added.

(4) The temperature at which the compound (2) is reacted with epihalohydrin (reaction temperature) may be appropriately adjusted according to the type of the compound in the reaction system, and may be, for example, 20 to 120 ° C.

時間 The time (reaction time) for reacting compound (2) with epihalohydrin may be appropriately adjusted according to other conditions such as the reaction temperature, and may be, for example, 0.5 to 10 hours.

反 応 The reaction in the above step 2 may be performed in the presence of a solvent. One type of solvent may be used alone, or two or more types may be used in combination. The solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, dimethyl sulfide, and trimethylamine. Is preferably diethyl ether, tetrahydrofuran, dimethyl sulfide or trimethylamine, and more preferably diethyl ether or tetrahydrofuran.

終了 After the epoxidation reaction, the reaction product may be washed with water, and then unreacted epihalohydrin and an organic solvent used in combination may be distilled off under heating and reduced pressure conditions. Further, in order to further reduce the hydrolyzable halogen in the reaction product, the reaction product is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and alkali metal water such as sodium hydroxide and potassium hydroxide is used. The reaction can be further performed by adding an aqueous solution of an oxide. At this time, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount thereof is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the reaction product. After completion of the epoxidation reaction, the generated salt is removed by filtration, washing with water, or the like, and the organic solvent is distilled off under reduced pressure under heating, whereby the compound (1) can be purified from the obtained reaction product.

≪Reactive diluent and composition≫
The compound (1) can be suitably used as a reactive diluent for adding to a resin component to lower the viscosity of the resin component.

That is, the reactive diluent according to the present invention is as follows.
A reactive diluent comprising the following component A,
Component A: a compound represented by the following general formula (1).

(In the formula (1), n is 0 or 1.)

The reactive diluent according to the present invention may be as follows.
A reactive diluent comprising the following component A,
Component A: a compound represented by the above general formula (1).

The reactive diluent is preferably liquid at 25 ° C. and has a viscosity at 25 ° C. of 0.01 to 1000 mPa · s, 1 to 300 mPa · s, or 5 to 35 mPa · s. s or 5.5 to 10 mPa · s. The viscosities are measured under the measurement conditions described in the examples or under compatible conditions to obtain the same results.
The compound represented by the general formula (1) is preferably liquid at 25 ° C., and has a viscosity at 25 ° C. of 0.01 to 1000 mPa · s, or 1 to 300 mPa · s. May be 5 to 35 mPa · s, or may be 5.5 to 10 mPa · s. The viscosities are measured under the measurement conditions described in the examples or under compatible conditions to obtain the same results.
The upper limit and the lower limit of the numerical value range of the viscosity exemplified above can be freely combined.

The resin component is not particularly limited, but an epoxy resin before curing, such as a monomer or a prepolymer, is preferable.

That is, the composition according to the present invention is as follows.
Composition containing the following components A and B Component A: a compound represented by the following general formula (1),

(In the formula (1), n is 0 or 1.)
Component B: a compound having two or more groups containing an epoxy ring in the molecule.

(4) The composition according to the present invention containing the component A and the component B may further contain a curing agent (component C), if necessary. The composition according to the present invention can further contain a curing accelerator (component D), a filler (component E), and the like, if necessary. Hereinafter, each component will be described.

<Component A>
The component A is a compound represented by the general formula (1) (the compound (1)), and is the same as that described in the above {Compound (1)}, and thus description thereof will be omitted. .

<Component B>
Component B is a compound having two or more groups containing an epoxy ring (for example, an epoxy group or a glycidyl group) in a molecule. Examples of the compound having two or more groups containing an epoxy ring in a molecule include a bifunctional or higher functional epoxy compound or an epoxy resin.
The compound having two or more groups containing an epoxy ring in the molecule may be a 2- to 10-functional epoxy compound, a 2- to 6-functional epoxy compound, or a 2- to 4-functional epoxy compound. Good.
The compound having two or more groups containing an epoxy ring in the molecule may be a bifunctional epoxy resin, a bifunctional epoxy resin, a bifunctional epoxy resin, or a bifunctional epoxy resin. Good.
A compound having two or more groups containing an epoxy ring in the molecule may be used as an epoxy resin by polymerizing and used as an epoxy compound or an epoxy resin having two or more groups containing an epoxy ring in the molecule. Are bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin; alicyclic epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin And novolak type epoxy resins such as aralkyl novolak type epoxy resins; diglycidyl etherified products of polyfunctional phenols; and hydrogenated products thereof. These epoxy resins may be used alone or in combination of two or more.
As the epoxy compound having two or more functions, an epoxy compound having three or more functions or an epoxy compound having four or more functions is preferable. The bifunctional or higher functional epoxy compound may be a bifunctional epoxy compound (compound having an epoxy ring-containing group having 2 to 10 in a molecule), a bifunctional hexafunctional epoxy compound, or a bifunctional epoxy compound. It may be a tetrafunctional epoxy compound.
As the bifunctional or higher functional epoxy resin, a trifunctional or higher functional epoxy resin or a tetrafunctional or higher functional epoxy resin is preferable. The bifunctional or higher functional epoxy resin may be a bifunctional epoxy resin (a compound having an epoxy ring-containing group of 2 to 10 in a molecule), a bifunctional hexafunctional epoxy resin, or a bifunctional epoxy resin. It may be a tetrafunctional epoxy resin.

As the compound having two or more groups containing an epoxy ring in the molecule, a trifunctional epoxy compound or a tetrafunctional epoxy compound is preferably used.
A typical trifunctional epoxy compound that can be used in the present invention includes a compound having the following structural formula (product name: TEPIC (registered trademark)).

典型 A typical tetrafunctional epoxy compound that can be used in the present invention includes a compound having the following structural formula (product name: jER (registered trademark) 1031S).

典型 A typical other tetrafunctional epoxy compound that can be used in the present invention is a naphthalene-type epoxy compound having the following structural formula ((product name: EPICLON EXA-4700)).

The mixing ratio (A: B) of component A and component B may be 1 to 80:20 to 99, 5 to 70:30 to 95, and 20 to 60:40 on a weight basis. It may be 80.
The total blending ratio of component A and component B in the composition may be 1 to 99% by weight, or 5 to 80% by weight, when the total weight of the entire composition is 100% by weight. , From 10 to 60% by weight.

<Component C>
Examples of the curing agent (component C) include various curing agents used as curing agents for epoxy compounds and epoxy resins. Examples of the curing agent include phenol-based curing agents, amine-based curing agents, acid anhydrides, boron trifluoride monoethylamine, isocyanates, dicyandiamide, and urea resins.
The phenolic curing agent may be any monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, for example, a novolak phenol resin such as a phenol novolak resin or a cresol novolak resin; a naphthalene phenol Phenol resins such as resin, high ortho-type novolak phenol resin, terpene-modified phenol resin, terpene phenol-modified phenol resin, aralkyl-type phenol resin, dicyclopentadiene-type phenol resin, salicylaldehyde-type phenol resin, and benzaldehyde-type phenol resin. Of these, phenol novolak resins, cresol novolak resins, and partially modified aminotriazine novolak resins are preferred.
Examples of the amine-based curing agent include aliphatic amines such as triethylenetetramine, tetraethylenepentamine and diethylaminopropylamine; and amine compounds such as aromatic amines such as metaphenylenediamine and 4,4'-diaminodiphenylmethane.
Examples of the acid anhydride include acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
These curing agents may be used alone or in combination of two or more.
The amount of the curing agent used is preferably such that the ratio of the reactive group equivalent of the curing agent to the epoxy equivalent of component A and component B is 0.3 to 1.5 equivalents. When the compounding amount of the curing agent is within the above range, the control of the degree of curing is easy and the productivity tends to be good.

<Component D>
Examples of the curing accelerator (component D) include an imidazole compound, an organic phosphorus compound, a tertiary amine, and a quaternary ammonium salt.
The imidazole compound may be an imidazole compound having a potential by masking a secondary amino group of imidazole with acrylonitrile, isocyanate, melamine, acrylate, or the like. Examples of the imidazole compound used herein include imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole , 4,5-diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-phenyl-4-methylimidazoline and the like.
Moreover, you may use the photoinitiator which produces | generates a radical, an anion, or a cation by photolysis and starts hardening.
These curing accelerators may be used alone or in combination of two or more.
The compounding amount of the curing accelerator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the components A and B. If it is at least the above upper limit, a better curing promoting effect will be obtained, and if it is at most the above lower limit, the composition tends to be excellent in storage stability and physical properties of the cured product, and also economically.

<Component E>
Examples of the filler (component E) include oxides such as silica, aluminum oxide, zirconia, mullite, and magnesia; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; aluminum nitride, silicon nitride, boron nitride, and the like. Nitrides; natural minerals such as talc, montmorillonite and saponite; metal particles and carbon particles. The average particle size of the inorganic filler is preferably 25 μm or less, more preferably 0.01 μm or more and 25 μm or less, further preferably 0.1 μm or more and 10 μm or less, and particularly preferably 0.3 μm or more and 7 μm or less. When the average particle size is not less than the lower limit, aggregation of the inorganic filler is easily suppressed, and the inorganic filler is easily dispersed in the resin. When the average particle size is equal to or less than the above upper limit, it is easy to suppress the wire from being damaged during the encapsulation molding. The average particle size means a 50% volume cumulative diameter (D50) measured by a particle size distribution meter (laser diffraction scattering method).
The amount of the filler is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, when the total weight of the whole composition is 100% by weight.

<Other components>
The composition according to the present invention may further contain, if necessary, other components that do not correspond to the above components A to E. Other components include other resins, solvents, additives, and the like.
Other resins include, for example, polyolefin, polyamide, polyimide and the like.

≫Applications of the composition≫
The composition according to the present invention can be suitably used for the following applications. When the composition according to the present invention is used after being cured, the composition preferably contains the components A to C, and more preferably the components A to D.

(Sealing material)
The composition according to the present invention can be used as a sealing material for components such as semiconductor components.
The sealing material according to the present invention includes the composition according to the present invention.
As the sealing material, for example, an aspect in which the space between the semiconductor component and the substrate, the periphery of the semiconductor component element is sealed with the sealing material, and an aspect in which the semiconductor component and the substrate are sealed with the sealing material (underfill ) Can be exemplified.
When the sealing material is used as an underfill, for example, the gap between the substrate and the semiconductor component can be filled with the sealing material by the following procedure. First, a sealing material is applied to one end of a semiconductor component while heating the substrate to 70 to 130 ° C. Then, the gap between the substrate and the semiconductor component is filled with the sealing material by capillary action. At this time, in order to shorten the time required for filling the sealing material, the substrate may be inclined, or a pressure difference may be generated between the inside and outside of the gap. After filling the gap with the sealing material, the gap can be sealed by heating and curing the sealing material.

(Substrate material)
The composition according to the present invention can be used as a substrate material.
For example, a substrate can be manufactured by impregnating fibers such as glass fiber and carbon fiber with the composition according to the present invention, molding the resultant into a sheet, obtaining a prepreg, and heating and curing the prepreg. . Two or more prepregs may be stacked.

≪cured product≫
The cured product according to the present invention is a cured product of the composition according to the present invention.
The cured product according to the present invention can be obtained, for example, by heating and curing the composition according to the present invention at 80 to 200 ° C. for 0.2 to 6 hours.

When the composition according to the present invention is a cured product, the composition preferably contains the components A to C, and more preferably the components A to D.

Further, as one embodiment of the present invention, a substrate provided with a cured product of the composition according to the present invention can be provided.
The substrate is provided with a cured product of the composition according to the present invention, and as described below, a cured product of a prepreg, a cured product of a resin sheet, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board. It may have at least one selected from the group consisting of:

As one embodiment of the present invention, a prepreg including the composition and the fiber according to the present invention can be provided.
Further, as one embodiment of the present invention, a resin sheet including the composition according to the present invention can be provided.

The resin sheet is obtained by molding the composition according to the present invention into a sheet, and the composition may be in a semi-cured state in order to enhance moldability. The resin sheet is suitably used as an interlayer insulating material.
The substrate may be provided with a cured product of a prepreg having the composition and fibers according to the present invention. Two or more prepregs described above may be stacked.
The substrate can be manufactured, for example, by heat-curing and pressing the prepreg described above.

Further, as one embodiment of the present invention, a copper-clad laminate in which a substrate and a copper foil are laminated can be provided. The copper foil of the copper clad laminate can be processed to form a circuit.
Therefore, as one embodiment of the present invention, a printed circuit board or a multilayer printed circuit board having a circuit formed on a board can be provided. The printed circuit board or the multilayer printed circuit board may further include a cured product of the resin sheet. A resin sheet may be provided instead of the substrate.

The copper-clad laminate can be manufactured by laminating the prepreg and the copper foil and forming the laminate under heat and pressure. The heating and pressing conditions can be appropriately adjusted according to the thickness of the copper-clad laminate to be manufactured or the composition of the composition according to the present invention.
A printed circuit board or a multilayer printed circuit board can be manufactured by a conventional method such as a plating through-hole method or a build-up method, and can be obtained by laminating the above-mentioned prepreg or insulating resin sheet on an inner-layer wiring board and performing heat and pressure molding. Can be. For example, after laminating copper foil on one or both sides of the prepreg according to the present invention, heat and press to produce a copper-clad laminate, open a hole in the copper-clad laminate, perform through-hole plating, and then perform plating. A printed circuit board or a multilayer printed circuit board can be manufactured by forming a circuit by etching a copper foil including a film.

The thickness of the prepreg, resin sheet, board, copper-clad laminate, printed circuit board, and multilayer printed circuit board is not particularly limited, but may be, for example, 0.1 to 10 mm, and may be, for example, 0.1 to 10 mm. It may be up to 5 mm.

(4) The cured product of the composition containing the reactive diluent according to the present invention has moderate flexibility. The cured product according to the present invention may have a flexural modulus value of 3000 MPa or less or 2500 MPa or less. Although the lower limit of the flexural modulus is not particularly limited, the value of the flexural modulus may be 1500 MPa or more, or 2000 MPa or more. The flexural modulus is assumed to be measured under the measurement conditions described in the examples or under compatible conditions that can provide the same result.

The cured product of the composition containing the reactive diluent according to the present invention has excellent dielectric properties.
The cured product according to the present invention may have a relative dielectric constant at 1 MHz or 1 GHz of 2 to 10, 2 to 5, or 3 to 4. The relative dielectric constant is assumed to be measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result.
The cured product according to the present invention may have a dielectric loss tangent at 1 MHz or 1 GHz of from 0.005 to 0.07, from 0.006 to 0.05, or from 0.007 to 0. 035 and may be 0.008 or more and less than 0.01. It is assumed that the dielectric loss tangent is measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result. The cured product having the above-mentioned dielectric properties may be read as a substrate, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board.
The cured product according to the present invention may have a water absorption value of 4% or less, 3% or less, or 1% or less. The lower limit of the water absorption is not particularly limited, but may be 0.5% or more. The fact that the water absorption is equal to or less than the above upper limit means that the cured product has excellent effect characteristics and that it has excellent water resistance or water repellency. The water absorption is assumed to be measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result.

Further, as one embodiment of the present invention, an electronic component including the cured product according to the present invention can be provided. More specifically, an electronic component in which a component such as a semiconductor component and a substrate are sealed with a cured product of the sealing material according to the present invention can be provided.
The electronic component may use, for example, a sealing material as an underfill, the space between the component and the substrate may be sealed with a sealing material, or the space between the component and the substrate, and around the component. It may be sealed with a sealing material.
Here, the components to be sealed include semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, capacitors, and the like, but are not limited thereto. The electronic component may include a terminal, a wire, a lead frame, other structures, and the like, in addition to the cured product of the substrate, the component, and the sealing material.

As described above, prepregs, resin sheets, substrates, copper-clad laminates, printed circuit boards, multilayer printed circuit boards, and electronic components can be manufactured from the composition according to the present invention. These have low dielectric properties, flexibility, and excellent heat resistance, and are used for mobile communication devices that handle high-frequency signals of 1 GHz or higher, base station devices, servers, electronic devices for networks such as routers, and large computers. The present invention can be suitably used for components of printed circuit boards for networks used in various electronic devices.

As described above, the embodiments of the present invention have been described in detail. However, each configuration in each embodiment and a combination thereof are only examples, and a combination of configurations, addition, omission, substitution, And other changes are possible. The present invention is not limited by each embodiment, but is limited only by the scope of the claims.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Synthesis of Compound>

[Synthesis Example 1]
A compound represented by the following formula (3-1) (sometimes abbreviated as “compound (3-1)”) and a compound represented by the following formula (3′-1) in a 1 L reaction vessel under an argon stream. 60 ml of dehydrated THF was added to 10 g (59.4 mmol) of a triisobutylene raw material (manufactured by TCI) containing the compound (may be abbreviated as “compound (3′-1)”) and stirred. Under ice-cooling, 9-BBN (89.1 mmol) was added dropwise at 10 ° C or lower, and after 30 minutes, the temperature was raised to 35 ° C. After stirring overnight, disappearance of the starting compound (3-1) was confirmed by gas chromatography (GC).

The reaction solution was ice-cooled again, and 79 ml (238 mmol) of 3M NaOHaq was added dropwise. Subsequently, a 30% by mass H ₂ O ₂ solution (80 ml) was added dropwise. After 17 hours, disappearance of the starting compound (3-1) was confirmed by GC.
After separating the organic layer and the aqueous layer, K ₂ CO ₃ was added to the organic layer, and water remaining in the organic solvent was separated. After separating the aqueous layer, the same operation was further performed twice. The aqueous layers were combined and extracted three times with ethyl acetate. Finally, the organic layers were combined and dried over MgSO ₄ . After filtering the desiccant, the solvent was distilled off under reduced pressure to obtain 18.22 g of a colorless transparent oily crude product. Unreacted internal olefin structure was removed during distillation under reduced pressure.
The crude product was roughly purified by distillation under reduced pressure (bath temperature: 100 ° C., top temperature: 45 ° C., degree of reduced pressure: 1.3 kPa), and then silica gel column (Silicagel: 92.8 g, eluent: Heptane / Ethyl acetate = 7/1). ) To obtain a white solid OH form. The yield was 2.74 g (14.7 mmol), the yield was 24.8%, and the GC purity was 99.9% or more. In addition, ¹ H-NMR was used to confirm that a compound represented by the following formula (2-1) (may be abbreviated as “compound (2-1)”) was synthesized.

The NMR data of the obtained compound (2-1) are shown below.
¹ H-NMR (300.40 MHz, CDCl ₃ , internal reference TMS)
0.92 (s, 18H), 1.15-1.41 (d, 4H), 1.57 (m, 1H), 3.53 (d, 2H), 7.28 (s, OH).

[Synthesis Example 2]
Next, in a 30 mL reaction vessel, 1.0 g (5.37 mmol) of the compound (2-1) synthesized in Synthesis Example 1, toluene, and tetrabutylammonium hydrogen were added.
After adding 73 mg (0.215 mmol) of Sulfate and 50% NaOHaq (5.4 mL) and purging with argon, the mixture was ice-cooled and stirred. 1.49 g (16.1 mmol) of epichlorohydrin was added dropwise thereto, and the mixture was stirred for 30 minutes and heated to room temperature. Two days later, the disappearance of the raw material compound (2-1-1) was confirmed by GC.
After quenching with water, the mixture was diluted with ethyl acetate. After separating the organic layer and the aqueous layer, the aqueous layer was extracted three times with ethyl acetate. The organic layers are combined and sat. Washed once with NaClaq and dried over Na ₂ SO ₄ . After filtering the drying agent, the solvent was distilled off under reduced pressure to obtain 1.94 g of a pale yellow oily crude product.
The crude product is purified by a Kugelrohr distillation apparatus (heating temperature: 160 to 240 ° C., degree of reduced pressure: 0.1 mmHg), and is a colorless, transparent and liquid compound represented by the following formula (1-1) according to the present invention ( "Compound (1-1)"). The yield was 770 mg (3.18 mmol), the yield was 59.2%, the GC purity was 95.8%, the viscosity was 5.8 mPa · s (25 ° C.), and the epoxy equivalent was 242. In addition, ¹ H-NMR was used to confirm that the compound (1-1) was synthesized.

The E-type viscosity at 25 ° C. was measured using the following E-type viscometer.
Equipment used: TV20 viscometer manufactured by Toki Sangyo Co., Ltd. Measurement temperature: 25 ° C
About 1.2 mL of the compound (1-1) was placed in a cup attached to an E-type viscometer, and the temperature of the cup was set to 25 ° C. The measurement of the rotational viscosity of the compound was started with an E-type viscometer, and the numerical value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.

The NMR data of the obtained compound (1-1) are shown below.
¹ H-NMR (300.40 MHz, CDCl _3, internal reference TMS)
0.92 (s, 18H), 1.15-1.36 (d, 4H), 1.74 (m, 1H), 2.61-2.77 (d, 2H), 3.14 (m, 1H), 3.40-3.67 (d, 18H), 3.38 ( t, 2H).

[Synthesis Example 3]
Instead of the triisobutylene raw material, a compound represented by the following formula (3-2) (sometimes abbreviated as “compound (3-2)”) and a compound represented by the following formula (3′-2) The reaction was carried out in the same manner as in Synthesis Example 1 except that a tetraisobutylene raw material (manufactured by TCI) containing a compound (may be abbreviated as “compound (3′-2)”) was used. -2) (in some cases, abbreviated as “compound (2-2)”) was synthesized.

The NMR data of the obtained compound (2-2) are shown below.
¹ H-NMR (300.40 MHz, CDCl ₃ , internal reference TMS)
0.87 (s, 6H), 0.92 (s, 9H), 0.97 (s, 9H), 1.02 (d, 2H), 1.17-1.41 (d, 4H), 1.60 (m, 1H), 3.50 (m, 2H) , 7.21 (s, OH).

[Synthesis Example 4]
The reaction was carried out in the same manner as in Synthesis Example 2 except that the compound (2-2) obtained above was used in place of the compound (2-1). The compound represented by 2) (may be abbreviated as “compound (1-2)”) was obtained. The overall yield of the compound (1-2) was 17.2%, GC purity was 98.2%, viscosity was 33 mPa · s (25 ° C.), and epoxy equivalent was 298. In addition, ¹ H-NMR was used to confirm that the compound (1-2) was synthesized. The viscosity of compound (1-2) was measured by the same method as in Synthesis Example 2.

The NMR data of the obtained compound (1-2) are shown below.
¹ H-NMR (300.40 MHz, CDCl _3, internal reference TMS)
0.87 (s, 6H), 0.92 (s, 9H), 0.97 (s, 9H), 1.02 (d, 2H), 1.15-1.36 (d, 4H), 1.74 (m, 1H), 2.64-2.79 (d, 2H), 3.17 (m, 1H), 3.42-3.69 (d, 2H), 3.36 (t, 2H).

[Synthesis Example 5]
The reaction was carried out in the same manner as in Synthesis Example 1 except that NH ₃ BH ₃ was used instead of 9-BBN, to synthesize the compound (2-1). Details are described below.

(NH ₃ BH ₃ synthesis)
First, NH ₃ BH ₃ was synthesized. The reagents used are as follows.
・ 7.57 g (200 mmol) of NaBH _{4
· (NH 4) 2 SO 4} 26.43g (200mmol)
・ THF 300ml
・ NH ₃ (Liquid specific gravity about 0.6) 7.9g
As a preliminary preparation, a 5% (v / v) NH ₃ / THF solution (200 ml) and a 1M NH ₃ / THF solution (100 ml) were prepared by blowing ammonia gas into THF under ice cooling.
Under air, a cooled 5% (v / v) NH ₃ / THF solution (200 ml) was charged into a 500 ml flask. Under ice-cooling, sodium borohydride and ammonium sulfate were added thereto, and the mixture was stirred at 0 ° C. for 2 hours and then at room temperature for 8 hours.
A 1M NH ₃ / THF solution (100 ml) was added to the obtained white suspension, and the mixture was stirred for 30 minutes, filtered through celite, and washed with THF. The obtained filtrate was concentrated and dried under reduced pressure at room temperature to obtain 4.73 g of NH ₃ BH ₃ as a white solid (yield: 76.6%, no impurity peak). ¹ B-NMR was used to confirm that NH ₃ BH ₃ was synthesized.

25.20 g (149.7 mmol) of a triisobutylene raw material (manufactured by TCI) containing compound (3-1) and compound (3′-1) in the air in a 200 mL reaction vessel, 25 ml of dehydrated THF, and NH ₃ BH ₃ 1.16 g (37.43 mmol) was added and stirred, and the reaction was carried out at 78 ° C. under reflux for 1 hour. Then, 10 ml of THF was distilled off from the reaction solution, and the mixture was reacted at 80 ° C. under reflux for 2 hours, followed by gas chromatography. (GC) confirmed the disappearance of the starting compound (3-1).

17 ml (49.9 mmol) of 3M NaOHaq was added to the reaction solution, and the mixture was heated under reflux at 73 ° C. for 3 hours. After cooling to 30 ° C., 17 ml (154.2 mmol) of a 30% by mass H ₂ O ₂ solution was added dropwise over 10 minutes. After the temperature was raised to 45 ° C, the mixture was stirred at room temperature overnight.
Purification was carried out in the same manner as in Synthesis Example 1 above, to obtain a white solid OH form. The yield was 6.7 g, the yield was 24.0%, and the GC purity was 99.0% or more. In addition, ¹ H-NMR was used to confirm that the compound (2-1) was synthesized.

<Preparation 1 of composition>
The following materials were blended at a blending ratio (parts by weight) shown in Table 1 to obtain a composition according to the present invention.

(Reactive diluent)
-Compound (1-1)
-Compound (1-2)
(Epoxy resin)
Epoxy resin I: phenol novolak type (liquid, epoxy equivalent 175 g / eq, viscosity 4500 Pa · s)
Epoxy resin II: bisphenol A liquid type (manufactured by Nippon Steel & Sumitomo Metal, model number: YD-128, epoxy equivalent 190 g / eq, viscosity 11,000 mPa · s) (curing agent)
Curing agent A: 2-ethyl-4-methylimidazole (amine equivalent: 110 g / eq) Curing agent B: phenol novolak resin (PR-HF-6, manufactured by Sumitomo Bakelite Co.) Curing agent C: methyl hexahydroanhydride phthalate Acid (curing accelerator)
Curing accelerator A: Triphenylphosphine (Hokuko TPP, manufactured by Hokuko Chemical Co., Ltd.) Curing accelerator B: 2-ethyl-4-methylimidazole (filler)
-Filler A: silicon dioxide powder-Filler B: boron nitride powder

<Evaluation>
(viscosity)
The E-type viscosity at 25 ° C. was measured using the following E-type viscometer.
Equipment used: Toki Sangyo Co., Ltd. TV20 viscometer Measurement temperature: 25 ° C
About 1.2 mL of each resin composition prepared in the formulation example was placed in a cup attached to an E-type viscometer, and the cup was set to a temperature of 25 ° C. The measurement of the rotational viscosity of the compound was started with an E-type viscometer, and the numerical value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.

(Tensile shear bond strength)
The tensile shear strength was measured under the following conditions.
After degreasing a Cu plate (length 150 mm × width 25 mm × thickness 1.5 mm) and an Al plate (length 150 mm × width 25 mm × thickness 1.5 mm) with acetone, each of the resin compositions prepared in the formulation examples was prepared. A thin brush was applied, and the Cu plate and the Al plate were overlapped with an overlap distance of 12.5 mm. Then, it was fixed with scissors and cured at 100 ° C. for 1 hour and 180 ° C. for 5 hours to prepare a test piece. The test was started at a tensile speed of 5 mm / min, and the load when the test piece was broken was defined as the tensile shear bond strength.

Table 1 shows the evaluation results.

<Preparation 2 of composition>
The following materials were blended at a blending ratio (parts by weight) shown in Table 2 to obtain a composition according to the present invention.

(Reactive diluent)
-Compound (1-1)
(Epoxy compound 1)
・ TEPIC-S (Nissan Chemical Industries, Ltd., epoxy equivalent: 100)
(Epoxy compound 2)
・ JER1031S (Mitsubishi Chemical Corporation, epoxy equivalent 196)
(Curing agent)
-MH-700 (MeHHPA, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 164)
(Curing accelerator)
・ Curesol (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.)

<Evaluation>
(Preparation of test pieces)
Reactive diluents, epoxy compounds, and curing agents were mixed in predetermined formulations shown in Table 2. Next, after adding and mixing a curing accelerator in a predetermined composition shown in Table 2, the mixture was poured into a casting cell. The casting cell was placed in a hot-air circulation oven, heated at 100 ° C. for 2 hours, and then cured at 150 ° C. for 5 hours to obtain a test piece.

(Bending test)
A bending test was performed under the following conditions.
・ Test method: JIS K 7171 compliant ・ Measurement items: strength, elastic modulus ・ Test specimen shape: 65 mm × 25 mm × 3 mm
・ Measurement conditions: Test speed: 1.5 mm / min
・ Distance between supporting points: 48mm
・ Number of measurements: n = 3
・ Test environment: 23 ℃ ± 1 ℃ ・ 50% RH ± 5% RH
-Measuring device: Universal material testing machine 5582 type (Instron)

(Relative permittivity and dielectric loss tangent)
The relative permittivity and the dielectric loss tangent were measured under the following conditions.
・ Test method: IEC 60250 compliant (automatic equilibrium bridge method) ・ Measurement items: relative permittivity ・ Dielectric loss tangent ・ Test piece shape: 60 mm × 60 mm × 3 mm
・ Measurement condition: Frequency; 1MHz
・ Measurement temperature: 23 ℃
・ Electrode dimensions: main electrode diameter φ36 mm, annular electrode inner diameter φ38 mm ・ Electrode material: conductive silver paint ・ Number of measurements: n = 2 (one sheet was measured twice)
-Condition adjustment: 23 ° C ± 2 ° C · 50% RH ± 5% RH for 48 hours · Test environment: 23 ° C ± 2 ° C · 50% RH ± 5% RH
-Measuring device: Precision LCR meter E4980A (manufactured by Agilent Technologies)

(Water absorption)
The water absorption was measured under the following conditions.
-Specimen shape: about 30mm x 40mm x 3mm
・ Pretreatment: 50 ° C, 24 hours (hot air circulation oven) ・ Test conditions: Boiling water (100 ° C), 100 hours ・ Number of measurements: n = 2

Table 2 shows the evaluation results.

<Preparation 3 of composition>
The following materials were blended at a blending ratio (parts by weight) shown in Table 3 to obtain a composition according to the present invention.

(Reactive diluent)
-Compound (1-1)
-Compound (1-2)
(Epoxy compound)
・ TEPIC-S (Nissan Chemical Industries, Ltd., epoxy equivalent: 100)
(Curing agent)
-MH-700 (MeHHPA, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 164)
(Curing accelerator)
・ Curesol (2E4MZ, manufactured by Shikoku Chemicals)
(filler)
・ Silica powder (25 μm average particle size)

<Manufacture of prepreg and printed circuit board>
Each resin composition prepared according to the formulation shown in Table 3 was impregnated into glass fibers and then dried at 165 ° C. for 3 to 10 minutes to produce a prepreg. After laminating 2 ply of the prepreg and an 18 μm-thick copper foil, the laminate was pressed to obtain a laminated thin plate having a thickness of 0.2 mm.

<Evaluation>
(Copper foil adhesion (Peel Strength: P / S))
According to the evaluation standard of IPC-TM-650 2.4.8, a circuit pattern (copper foil) formed on a printed circuit board obtained by impregnating the laminated thin plate with a copper etchant and removing the copper foil was 90%. It was pulled up in the ° direction, and the peeling time of the circuit pattern was measured and evaluated (kgf / cm).

(Moisture absorption heat resistance evaluation (PCT))
The printed circuit board was allowed to stand at 121 ° C. and 0.2 MPa for 4 hours using a pressure cooker tester (ESPEC, EHS-411MD), and then was dipped at a solder 288 ° C. every 10 seconds. Then, the time until the delamination phenomenon between the insulating layer and the copper foil, between the insulating layer and the metal core, or between the insulating layers occurred was measured and evaluated.
The test was passed in 2 hours or more.

(Relative permittivity and dielectric loss tangent)
The relative permittivity and the dielectric loss tangent of the printed circuit board were measured at a frequency of 1 GHz using a relative dielectric constant measuring device (RF Impedance / Material Analyzer: manufactured by Agilent).

Table 3 shows the evaluation results.

From the results shown above, it is understood that the compound according to the present invention can be suitably used as a reactive diluent mixed with an epoxy resin. The resin composition containing the compound according to the present invention has a reduced viscosity, and the cured product of the resin composition exhibits excellent dielectric properties, has good flexibility, and is externally applied with force. It has been found that it has an excellent property that it is hard to break even when it is broken.

Claims (12)

1. A reactive diluent comprising the following component A,
   Component A: a compound represented by the following general formula (1).
   

   

   (In the formula (1), n is 0 or 1.)
2. A composition comprising the following components A and B,
   Component A: a compound represented by the following general formula (1),
   

   

   (In the formula (1), n is 0 or 1.)
   Component B: a compound having two or more groups containing an epoxy ring in the molecule.
3. The composition according to claim 2, further comprising the following component C:
   Component C: curing agent.
4. The composition according to claim 3, further comprising the following component D:
   Component D: curing accelerator.
5. 封 止 A sealing material containing the composition according to claim 3.
6. 硬化 A cured product of the composition according to claim 3 or 4.
7. A substrate comprising the cured product according to claim 6.
8. An electronic component comprising the cured product according to claim 6.
9. A compound represented by the following general formula (1).
   

   

   (In the formula (1), n is 0 or 1.)
10. A compound represented by the following general formula (2).
    

    

    (In the formula (2), n is 0 or 1.)
11. A method for producing a compound represented by the following general formula (2), comprising hydroxylating a compound represented by the following general formula (3) to obtain a compound represented by the following general formula (2).
    

    

    (In the formula (3), n is 0 or 1.)
    

    

    (In the formula (2), n is 0 or 1.)
12. A method for producing a compound represented by the following general formula (1), comprising epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1).
    

    

    (In the formula (2), n is 0 or 1.)
    

    

    (In the formula (1), n is 0 or 1.)