WO2018123806A1

WO2018123806A1 - Alkenyl-group-containing resin, curable resin composition, and cured article thereof

Info

Publication number: WO2018123806A1
Application number: PCT/JP2017/045930
Authority: WO
Inventors: 窪木　健一; 一貴松浦
Original assignee: 日本化薬株式会社
Priority date: 2016-12-26
Filing date: 2017-12-21
Publication date: 2018-07-05
Also published as: JP6963565B2; JPWO2018123806A1; TWI739976B; TW201833163A

Abstract

The present invention provides: an alkenyl-group-containing resin, a cured article thereof having exceptional low moisture absorbency (low water absorbency) and heat resistance; a curable resin composition; and a cured article thereof. In this alkenyl-group-containing resin, which is represented by formula (1), 20% or more of the alkenyl groups in the plurality of X and Y moieties are propenyl groups. (In the formula, the plurality of Z moieties each independently represent a C6-15 hydrocarbon group. The plurality of X moieties each independently represent a hydrogen atom, a C1-6 alkyl group, an allyl group, a propenyl group, or a glycidyl group, excluding when all of the plurality of X moieties are hydrogen atoms or allyl groups. The plurality of Y moieties each independently represent a hydrogen atom, a C1-6 alkyl group, an allyl group, or a propenyl group. N represents the number of repetitions, and the average value thereof is a real number of 1 to 20)

Description

Alkenyl group-containing resin, curable resin composition and cured product thereof

The present invention relates to an alkenyl group-containing resin, a curable resin composition, and a cured product thereof, a semiconductor element sealing material, a liquid crystal display element sealing material, an organic EL element sealing material, a printed wiring board, It is suitably used for lightweight and high-strength composite materials for electrical and electronic parts such as build-up laminates, carbon fiber reinforced plastics, and glass fiber reinforced plastics.

In recent years, the required characteristics of a laminated board on which electric / electronic components are mounted have been widened and advanced with the expansion of the field of use. For example, conventionally, a semiconductor chip has been mainly mounted on a metal lead frame, but a semiconductor chip having a high processing capability such as a central processing unit (hereinafter referred to as “CPU”) is made of a polymer material. More and more are mounted on the laminates that are made. As the processing speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become a problem, and low dielectric constant and low dielectric loss tangent are required for wiring boards. Yes. At the same time, as the processing speed of the device is increased, the heat generated by the chip is increased, so that it is necessary to improve the heat resistance.
In recent years, mobile electronic devices such as smartphones have become widespread, and precision electronic devices are being used and carried in the outdoor environment and very close to the human body. Tolerance is required.
Furthermore, in the automotive field, electronic technology has progressed, and precision electronic equipment may be placed near the engine, which requires higher levels of heat and humidity resistance. Trains, air conditioners, etc. SiC semiconductors have begun to be used, and high heat resistance is required for the sealing material of the semiconductor element, which cannot be handled by the conventional epoxy resin sealing material.
In recent years, the weight reduction of airplanes, automobiles, trains, ships, etc. has progressed due to the need for energy saving. In the field of vehicles, studies have been made in particular in the field of vehicles in which a metal material is replaced with a lightweight and high-strength carbon fiber composite material. For example, in Boeing 787, the weight ratio is reduced by increasing the ratio of the composite material, and the fuel efficiency is greatly improved. In the automotive field, although it is a part, it is equipped with a shaft made of composite material, and there is also a movement to make the car body with composite material for luxury cars. In response to these demands, many proposals have been made mainly for epoxy resins and resin compositions containing them, but since the demand for application of composite materials has gradually started around engines, maleimide resins and the like have been studied. (Patent Documents 3 and 4). Patent Document 1 discloses a resin composition of a maleimide resin and a propenyl group-containing phenol resin. Patent Document 2 discloses a resin composition of a maleimide resin and an unsubstituted allyl ether-modified phenol resin or a phenol resin substituted with allyl groups.

Japanese Laid-Open Patent Publication No. 04-359911 International Publication No. 2016/002704 Japanese Unexamined Patent Publication No. 2009-001783 Japanese Laid-Open Patent Publication No. 01-294661

However, since Patent Document 1 uses a phenol resin substituted with a propenyl group, the hygroscopic property is poor, and accordingly, the electrical characteristics are insufficient. In addition, Patent Document 2 uses a phenol resin substituted with allyl groups, so that the reactivity is poor and the hygroscopic property is poor, and the performance is still not sufficient, and further improvement is required. Therefore, the present invention provides an alkenyl group-containing resin, a curable resin composition, and a cured product thereof that exhibit excellent hygroscopicity (low water absorption) and heat resistance in the cured product.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention

[1] An alkenyl group-containing resin represented by the following formula (1), wherein 20% or more of a plurality of alkenyl groups in X and Y are propenyl groups,

(Wherein a plurality of Z's each independently represents a hydrocarbon group having 6 to 15 carbon atoms. A plurality of X's each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, propenyl) Represents a group or a glycidyl group, except for the case where all of a plurality of X are hydrogen atoms or allyl groups, each of the plurality of Y independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or Represents a propenyl group, n represents the number of repetitions, and the average value is a real number of 1 to 20.)
[2] The alkenyl group-containing resin according to [1], wherein a plurality of Xs in the formula (1) are allyl groups, propenyl groups, or glycidyl groups, and all Xs are not allyl groups,
[3] The alkenyl group-containing resin according to [1] or [2], in which 20% or more of the plurality of Xs in the formula (1) are alkenyl groups.
[4] The alkenyl group-containing resin according to any one of [1] to [3], wherein Z in the formula (1) is an aromatic-containing hydrocarbon group,
[5] The alkenyl group-containing resin according to any one of [1] to [4], wherein Z is a hydrocarbon group having 10 to 15 carbon atoms in the formula (1),
[6] A curable resin composition containing the alkenyl group-containing resin according to any one of [1] to [5],
[7] The curable resin composition according to [6] above, which contains a radical polymerization initiator,
[8] The curable resin composition according to [6] or [7] above, which contains a maleimide compound,
[9] A cured product obtained by curing the curable resin composition according to any one of [6] to [8],
Is provided.

The cured product of the resin composition using the alkenyl group-containing resin of the present invention exhibits excellent low moisture absorption (low water absorption) and heat resistance (solder reflow resistance). Therefore, insulating materials for electrical and electronic parts (such as highly reliable semiconductor sealing materials) and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), liquid crystal sealing materials, EL sealing materials, adhesives (conductive) Adhesives, etc.), various composite materials including CFRP, and paints.

Hereinafter, the present invention will be described in detail.
The alkenyl group-containing resin of the present invention is represented by the following formula (1).

(Wherein a plurality of Z's each independently represents a hydrocarbon group having 6 to 15 carbon atoms. A plurality of X's each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, propenyl) Represents a group or a glycidyl group, except for the case where all of a plurality of X are hydrogen atoms or allyl groups, each of the plurality of Y independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or Represents a propenyl group, n represents the number of repetitions, and the average value is a real number of 1 to 20.)

In the alkenyl group-containing resin of the present invention, all or part of the allyl group is converted into a more reactive propenyl group, and as a result, a reaction between the propenyl groups occurs in the curing process, so that the crosslinking density increases. Heat resistance (glass transition temperature) is improved. On the other hand, when mixed with a reactive olefin resin such as a maleimide group or an acrylate group, the propenyl group is more likely to proceed than the allyl group. Further, unlike the reaction of epoxy groups, polar groups are not generated, so that the increase in water absorption (wetness) accompanying the improvement in heat resistance can be reduced.

In the alkenyl group-containing resin of the present invention, in the formula (1), each X independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group (—CH ₂ —CH═CH ₂ ), a propenyl group ( —CH═CH—CH ₃ ) or a glycidyl group, and each Y independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group (—CH ₂ —CH═CH ₂ ) or a propenyl group (—CH = CH-CH ₃ ), and from the viewpoint of heat resistance and hygroscopicity, 20% or more of all alkenyl groups (that is, the total of allyl groups and propenyl groups) are propenyl groups, more preferably 40% or more, Particularly preferably, it is 50% or more. Further, all of the alkenyl groups may be propenyl groups.
The proportion of propenyl groups in all alkenyl groups can be measured by nuclear magnetic resonance (hereinafter referred to as “NMR”).

However, the case where all of a plurality of X in the formula (1) are hydrogen atoms or allyl groups is excluded. For example, in the case of a compound in which all of a plurality of Xs in the formula (1) are hydrogen atoms and all of the plurality of Ys are propenyl groups, the hydroxyl groups remain in the cured product or reacted with an epoxy. As a result, an alcoholic hydroxyl group is generated, so that the hygroscopic property is high, and the electrical characteristics may be deteriorated accordingly.
In the case of an allyl ether-modified biphenylaralkyl novolak resin in which all of a plurality of X in the formula (1) are allyl groups and all of the plurality of Ys are hydrogen atoms, the allyl ether group is very reactive. , The curing may be slow and productivity may be deteriorated. Moreover, since high temperature is required for hardening, an allyl ether group rearranges during hardening and a hydroxyl group is generated, which may adversely affect low hygroscopicity.
Furthermore, in the case of a compound in which all of a plurality of X in the formula (1) are hydrogen atoms and all of the plurality of Ys are allyl groups, the allyl group is poor in reactivity, so that the curing is slowed and produced. May be worse. Further, since the hydroxyl group remains in the cured product as it is or reacts with epoxy to produce an alcoholic hydroxyl group, the hygroscopic property is high, and the electrical characteristics may be deteriorated accordingly.
For the above reasons, X and Y are preferably alkenyl groups. The alkenyl groups in X and Y are each preferably 20% or more, more preferably 40% or more, and particularly preferably 60% or more.

In the above formula (1), if 20% or more of the alkenyl groups in plural X and Y are propenyl groups, a part of the plural X and Y may be alkyl groups having 1 to 6 carbon atoms. Good. Examples of the alkoxy group having 1 to 6 carbon atoms include alkyl groups having a linear, branched or cyclic structure such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.

In the formula (1), a plurality of Z each independently represents a hydrocarbon group having 6 to 15 carbon atoms. An aromatic hydrocarbon group is preferable, and a hydrocarbon group having 10 to 15 carbon atoms is particularly preferable.
Specific examples of Z in the formula (1) include the following structures, but are not limited thereto.

In the above formula (1), the average value of n is 1 to 20, preferably 1 to 10, particularly preferably 1 to 6.

In the formula (1), when X contains a glycidyl group, the epoxy equivalent of the alkenyl group-containing resin of the present invention is 210 to 5000 g / eq. And more preferably 210 to 3000 g / eq. It is. Epoxy equivalent is 5000 g / eq. The following indicates that the amount of epoxy groups per unit structure does not decrease, which means that the number of epoxy groups does not decrease. Therefore, it is preferable in terms of heat resistance.

The total amount of chlorine remaining in the alkenyl group-containing resin of the present invention is preferably 1500 ppm or less, more preferably 1000 ppm or less, and particularly preferably 500 ppm or less.

Next, the manufacturing method of the alkenyl group containing resin of this invention is demonstrated.
First, the alkenyl group-containing resin of the present invention uses a phenol resin of the following formula (2) as a raw material.

(Wherein a plurality of Z's each independently represent a hydrocarbon group having 6 to 15 carbon atoms. A plurality of Y's each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group or a propenyl) And n represents the number of repetitions, and the average value is a real number of 1 to 20.)

The alkenyl group-containing resin of the present invention can be produced by combining two or more of the following reaction steps.
a) Allylation reaction of hydroxyl group in formula (2) (synthesis of allyl ether)
b) Glycidylation reaction of hydroxyl group in formula (2) c) Rearrangement reaction of allyl ether body to propenyl ether body d) Claisen rearrangement reaction of allyl ether body (synthesis of allylated phenol resin)
e) Rearrangement reaction of allyl group to propenyl group

Hereinafter, each reaction process is explained in full detail.
a) Allylation reaction of hydroxyl group (synthesis of allyl ether)
The reaction of allylating (allyl etherifying) the hydroxyl group of the phenol resin represented by the formula (2) can be carried out by a known method. Generally, allyl chloride or base using a base such as an alkali metal hydroxide is used. Allyl halides such as allyl bromide and allyl iodide are reacted to form an allyl ether.
At this time, a highly polar solvent such as methanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone is used. It is preferable to use it. The amount of the polar solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass with respect to 100 parts by mass of the raw material phenol resin. These may be used alone or in combination, and a solvent having low polarity such as toluene or xylene may be used in combination.
The amount of allyl halide and base used is usually 0.1 to 2.0 mol, preferably 0.2 to 1.5 mol, based on 1 equivalent of the hydroxyl group of the phenol resin. The rate can be adjusted.
For example, more specifically, after the phenol resin is dissolved in the aforementioned isopropanol or dimethyl sulfoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, and the alkali metal hydroxide is added at 50 to 100 ° C. After dissolution, allyl chloride or allyl bromide is added at 30 to 50 ° C. over 2 to 5 hours, and then reacted at 30 to 70 ° C. for 1 to 10 hours. After completion of the reaction, toluene, methyl isobutyl ketone, etc. are added, and the by-produced salt is removed by filtration, washing with water, etc., and further, an allyl ether form is obtained by distilling off solvents such as toluene, methyl isobutyl ketone, etc. under heating and reduced pressure. Can do.

b) Glycidylation of hydroxyl group in formula (2) (synthesis of epoxy resin)
The reaction for glycidylating the hydroxyl group of the phenolic resin in the formula (2) is a known method, and is generally performed using a base such as an alkali metal hydroxide such as epichlorohydrin, epibromohydrin, epiiodohydrin, etc. Epihalohydrin is reacted to glycidyl ether.
For example, a mixture of a phenol resin and an epihalohydrin is reacted at 20 to 120 ° C. for 1 to 20 hours while adding an alkali metal hydroxide solid such as sodium hydroxide or potassium hydroxide all at once or gradually. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution. In that case, the alkali metal hydroxide is continuously added and water and epihalohydrins are continuously added under reduced pressure or normal pressure from within the reaction system. The water may be removed and the epihalohydrins may be continuously returned to the reaction system.
In the above method, the amount of epihalohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, per 1 equivalent of the hydroxyl group of the phenol resin. The amount of the alkali metal hydroxide used is usually in the range of 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol, per 1 equivalent of the hydroxyl group of the phenol resin.
In the above reaction, an epoxy resin having a low hydrolyzable halogen concentration can be obtained by adding an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide (DMSO), dimethylformamide, 1,3-dimethyl-2-imidazolidinone. can get. For example, the total chlorine concentration is preferably 1500 ppm or less, more preferably 1000 ppm or less. The amount of the aprotic polar solvent used is in the range of 5 to 200 parts by mass, preferably 10 to 100 parts by mass with respect to the mass of the epihalohydrins. In addition to the above solvent, the reaction can easily proceed by adding alcohols such as methanol and ethanol. In addition, toluene, xylene, dioxane and the like can also be used.
Usually, these reactants are washed with water, or after removing excess epihalohydrin under heating and reduced pressure without washing with water, and then dissolved in a solvent such as toluene, xylene, methyl isobutyl ketone, and the like. The reaction is carried out again by adding an aqueous solution of an alkali metal hydroxide. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol, relative to 1 equivalent of the hydroxyl group of the phenol resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
After completion of the reaction, the by-produced salt is removed by filtration, washing with water, etc., and an epoxy resin with less hydrolyzable halogen can be obtained by distilling off a solvent such as toluene, xylene, methyl isobutyl ketone under heating and reduced pressure.

c) Rearrangement reaction of allyl ether group to propenyl ether The rearrangement reaction of the allyl ether group to the propenyl ether group can be carried out by a known method and is generally carried out using a strong base in a polar solvent. Examples of the polar solvent used include, but are not limited to, methanol, isopropanol, dimethylsulfone, dimethylsulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Ketone solvents are not suitable because they use strong bases as catalysts. The amount of the polar solvent used is usually 20 to 400 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of the raw material. These may be used alone or in combination. A solvent may be used in combination. Strong bases include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, tetramethylammonium hydroxide and the like. The amount of strong base used varies greatly depending on the type of solvent used, the type of base, etc., but is usually 0.1-3.0 mol, preferably 0.2-2. The range is 0 mol.
For example, in more detail, a compound having an allyl ether group is dissolved in dimethyl sulfoxide and the like, potassium-tert-butoxide is added, and the mixture is reacted at 30 to 80 ° C. for 2 to 10 hours. After completion of the reaction, neutralize, add toluene, methyl isobutyl ketone, etc., remove the neutralized salt by washing with water, etc., and further distill off the solvent such as toluene, methyl isobutyl ketone, etc. Obtainable. The conversion rate to the propenyl ether group can also be adjusted by adjusting the type and amount of strong base, reaction temperature, and reaction time.

d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)
The Claisen rearrangement reaction may be carried out according to a conventional method. For example, a compound having an allyl ether group is heated to 150 to 230 ° C. in the presence or absence of a high-boiling solvent such as carbitol, paraffin oil, N, N′-dimethylaniline. For 0.5 to 100 hours. The solvent is used in an amount of 10 to 200 parts by mass based on 100 parts by mass of allyl ether. After completion of the reaction, the solvent used can be removed if necessary to obtain an allylated phenol resin.
In the Claisen rearrangement reaction, the reaction is preferably performed in a vacuum or in an inert gas atmosphere such as nitrogen or argon, and the product can be prevented from being colored. However, it is difficult to maintain a complete vacuum or inert gas atmosphere, and it is inevitable that a trace amount of oxygen is mixed into the system. For this reason, it is preferable to carry out Claisen rearrangement by adding an antioxidant. The antioxidant is preferably used in an amount of about 10 parts by mass with respect to 100 parts by mass of allyl ether. Phenol antioxidants include methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tert-butylated bisphenol A, 2,2'-methylenebis (4-methyl- 6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-ethylidenebis (3-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) buta 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1-bis (4-hydroxyphenyl) -cyclohexane, etc. However, it is not limited to these. These may be used alone or in combination of two or more, but it is preferable to use a compound having two or more phenolic hydroxyl groups per molecule. The conversion rate to the propenyl group can also be adjusted by adjusting the reaction temperature and reaction time.

e) Rearrangement reaction of an allyl group to a propenyl group The rearrangement reaction of an allyl group to a propenyl group can be performed by a known method, and is generally carried out in a polar solvent using a strong base. Examples of the polar solvent used include, but are not limited to, methanol, isopropanol, dimethylsulfone, dimethylsulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Ketone solvents are not suitable because they use strong bases as catalysts. The amount of the polar solvent used is usually 20 to 400 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of the raw material. These may be used alone or in combination. A solvent may be used in combination. Strong bases include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, tetramethylammonium hydroxide and the like. The amount of strong base used varies greatly depending on the type of solvent used, the type of base, etc., but is usually 0.1-3.0 mol, preferably 0.2-2. The range is 0 mol.
For example, more specifically, an allyl group-containing compound is dissolved in methanol, dimethyl sulfoxide or the like, and then sodium hydroxide and potassium hydroxide are added and reacted at 50 to 150 ° C. for 2 to 10 hours. After completion of the reaction, neutralize, add toluene, methyl isobutyl ketone, etc., remove the neutralized salt by washing with water, etc., and further distill off the solvent such as toluene, methyl isobutyl ketone, etc. under heating and reduced pressure to have a compound having a propenyl group Can be obtained. The conversion rate to the propenyl ether group can also be adjusted by adjusting the amount of strong base, reaction temperature, and reaction time.

The alkenyl group-containing resin of the present invention can be produced by combining two or more of the above reaction steps a) to e).

The alkenyl group-containing resin having a glycidyl group of the present invention can also be used as a raw material for epoxy acrylate resins.

The curable resin composition of the present invention contains the alkenyl group-containing resin of the present invention, and can further contain a compound having a functional group that reacts by heating.
The content of the alkenyl group-containing resin in the curable resin composition of the present invention is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more.

The curable resin composition of the present invention may contain a maleimide compound.
A conventionally well-known maleimide compound can be used as a maleimide compound which can be mix | blended with the curable resin composition of this invention. Specific examples of the maleimide compound include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3 '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like, but are not limited thereto. These may be used alone or in combination of two or more. The blending amount of the maleimide compound is preferably 5 times or less, more preferably 2 times or less in terms of mass ratio.
In addition, maleimide compounds described in Japanese Patent Application Laid-Open No. 2009-001783 (Patent Document 3) and Japanese Patent Application Laid-Open No. 01-294661 (Patent Document 4) have low hygroscopicity, flame retardancy, and dielectric properties. Since it is excellent in characteristics, it is particularly preferable as a maleimide compound.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator for reacting alkenyl groups of the alkenyl group-containing resin of the present invention with each other or between an alkenyl group and a maleimide group. Specific examples of the radical polymerization initiator that can be used include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctate, and t-butyl peroxy. Organic peroxides such as benzoate and lauroyl peroxide, azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile), etc. Although the well-known hardening accelerator of an azo type compound is mentioned, It does not specifically limit to these. The amount is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may contain an epoxy resin. As an epoxy resin that can be blended in the curable resin composition of the present invention, any conventionally known epoxy resin can be used. Specific examples of epoxy resins include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, polycondensates of bisphenols and various aldehydes. And glycidyl ether epoxy resins obtained by glycidylation of alcohols, alicyclic epoxies such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4′-epoxycyclohexanecarboxylate Examples of the resin include, but are not limited to, glycidylamine epoxy resins and glycidyl ester epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol. These may be used alone or in combination of two or more.
Further, a phenol aralkyl resin obtained by condensation reaction of phenols and the above-mentioned bishalogenomethyl aralkyl derivative or aralkyl alcohol derivative, and an epoxy resin obtained by dehydrochlorination reaction with epichlorohydrin are low hygroscopic, Since it is excellent in a flame retardance and a dielectric characteristic, it is especially preferable as an epoxy resin.

When the curable resin composition of the present invention contains an epoxy resin, an epoxy resin curing catalyst (curing accelerator) can be blended as necessary. For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, Amines such as triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine, Examples thereof include phosphines such as tributylphosphine and trioctylphosphine. The compounding amount of the curing catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the curable resin composition.

When the alkenyl group-containing resin of the present invention contains a glycidyl group or contains the above-mentioned epoxy resin, the curable resin composition of the present invention contains various epoxy resin curing agents in its preferred embodiment.
As the epoxy resin curing agent, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substituted) Polymerization of phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols and various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, imidazole, BF 3 _- amine complex, guanidine derivatives. The amount of the epoxy resin curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents per 1 equivalent of epoxy group (or glycidyl group). If it is 0.5 equivalent or more or 1.5 equivalent or less with respect to 1 equivalent of epoxy groups, hardening will become more reliable and more favorable hardened | cured material property will be obtained.

The curable resin composition of the present invention may contain a cyanate ester resin. A conventionally well-known cyanate ester compound can be used as a cyanate ester compound which can be mix | blended with the curable resin composition of this invention. Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Examples thereof include, but are not limited to, cyanate ester compounds obtained by reacting a product with cyanogen halide. These may be used alone or in combination of two or more.
Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.
Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde.
Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene.
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
Specific examples of the cyanate ester compound include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl). ) Methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2'-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2'-bis (4-sia Natophenyl) ethane, 2,2′-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether, phenol novolac cyanate, phenol di Examples include those in which the hydroxyl group of the cyclopentadiene cocondensate is converted to a cyanate group. It is not limited to that.
In addition, cyanate ester compounds described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferable as cyanate ester compounds because they are excellent in low moisture absorption, flame retardancy, and dielectric properties.

When the curable resin composition of the present invention contains a cyanate resin, a naphthenic acid zinc, a cobalt naphthenate, a copper naphthenate, Catalysts such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, and dibutyltin maleate can also be included. The catalyst is generally used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, with respect to 100 parts by mass of the total mass of the thermosetting resin composition.

Further, the curable resin composition of the present invention includes fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia as necessary. Add powders such as aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, or inorganic fillers in which these are spherical or crushed. Can do. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is usually in the range of 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. is there.

In the curable resin composition of the present invention, known additives can be blended as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, silane coupling agents, and the like. Coloring agents such as surface treatment agents, release agents, carbon black, phthalocyanine blue, and phthalocyanine green can be used. The compounding amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less with respect to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention is obtained by uniformly mixing each of the above components at a predetermined ratio, and is usually precured at 130 to 180 ° C. for 30 to 500 seconds, and further 150 to 200 ° C. And after curing for 2 to 15 hours, a sufficient curing reaction proceeds and the cured product of the present invention is obtained. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed and then cured.

The cured product of the present invention thus obtained has moisture resistance, heat resistance, and high adhesiveness. Therefore, the epoxy resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance and high adhesion. Specifically, it is useful as a material for all electrical and electronic components such as an insulating material, a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, and a resist. In addition to molding materials and composite materials, they can also be used in fields such as paint materials and adhesives. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.

The semiconductor device has a cured product of the curable resin composition of the present invention such as one sealed with the curable resin composition of the present invention. As semiconductor devices, for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).

An organic solvent can be added to the curable resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned. The solvent is used in the range where the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by mass, preferably 20 to 70% by mass.

The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed evenly or prepolymerized. For example, the alkenyl group-containing resin and the maleimide resin are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, an alkenyl group-containing resin and a maleimide resin may be prepolymerized by adding an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives as necessary. For mixing or prepolymerization of each component, in the absence of a solvent, for example, an extruder, a kneader, a roll or the like is used, and in the presence of a solvent, a reaction kettle with a stirrer is used.

A prepreg can be obtained by heating and melting the curable resin composition of the present invention to lower the viscosity and impregnating the fiber with a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber.
Moreover, a prepreg can also be obtained by impregnating the varnish into a reinforcing fiber and drying by heating.
The above prepreg is cut into a desired shape, laminated with copper foil as necessary, and then the curable resin composition is heated and cured while applying pressure to the laminate by a press molding method, autoclave molding method, sheet winding molding method, etc. Thus, an electric / electronic laminate (printed wiring board) and a carbon fiber reinforcing material can be obtained.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the examples, epoxy equivalent, melt viscosity, softening point, and total chlorine concentration were measured under the following conditions.
Epoxy equivalent: Measured by a method according to JIS K-7236.
Melt viscosity: Melt viscosity in the cone plate method.
Softening point: Measured by a method according to JIS K-7234.
Propenyl group ratio in all alkenyl groups: measured by NMR.
Total chlorine: automatic sample combustion-ion chromatograph AQF-2100H type manufactured by Mitsubishi Chemical Corporation Ion content was measured after combustion decomposition with an argon gas flow rate of 200 ml / min and an oxygen gas flow rate of 400 ml / min.

Reference example 1
A phenolic resin represented by the following formula (3) (hereinafter referred to as “BPN”, a softening point of 74 ° C., a melt viscosity of 0.16, and a hydroxyl group equivalent of 210 g / eq) is attached to a flask equipped with a thermometer, a condenser, and a stirrer. 210 parts by mass, 380 parts by mass of dimethyl sulfoxide, 30 parts by mass of water and 45 parts by mass of flaky sodium hydroxide were added, heated, stirred and dissolved, and then 3 parts by mass of 102 parts of allyl chloride were maintained at a temperature of 40 ° C. Added continuously over time. After the addition of allyl chloride, the reaction was carried out at 45 ° C. for 1 hour and at 60 ° C. for 1 hour. Subsequently, dimethyl sulfoxide was distilled off under heating and reduced pressure, and 250 parts by mass of methyl isobutyl ketone was added to the residue to dissolve the residue. After adding water to this methyl isobutyl ketone solution and removing by-product salts by standing and liquid separation, washing with water was repeated until the waste liquid became neutral. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 243 parts by mass of an allyl ether of BPN (hereinafter referred to as “BPN-AE”). The above reaction corresponds to the above-mentioned “a) hydroxylation reaction of hydroxyl group in the formula (2) (synthesis of allyl ether form)”. In the obtained BPN-AE, X in the formula (1) is an allyl group, and Y is a hydrogen atom.

(In the formula, n is an average value and represents a real number of 1 to 20.)

Reference example 2
200 parts by mass of BPN-AE obtained in Reference Example 1 was charged into a reaction vessel, heated with stirring, and reacted at 200 ° C. for 5 hours, whereby allylated BPN (hereinafter referred to as “BAPN”) 199. A mass part was obtained. The above reaction corresponds to the aforementioned “d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)”. In the obtained BAPN, X in the formula (1) is a hydrogen atom, and Y is an allyl group.

Reference example 3
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 227 parts by mass of BAPN obtained in Reference Example 2, 227 parts by mass of methanol, and 35 parts by mass of toluene, and heated and stirred to dissolve. Next, 90 parts by mass of marbled potassium hydroxide (purity 85%) was added, and the temperature was raised while distilling off methanol and toluene. When the temperature reached 100 ° C., the system was switched to the reflux line, and the reaction was carried out at the same temperature for 20 hours. went. After completion of the reaction, 50 parts by mass of methanol was added, and 143 parts by mass of concentrated hydrochloric acid was added for neutralization. 200 parts by mass of toluene was added, and after standing, the separated lower aqueous layer was removed, and then washing with water was repeated until the aqueous layer became neutral. Subsequently, 228 parts by mass of propenylated BPN (hereinafter referred to as “BPPN”) was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The above reaction corresponds to the above-mentioned “e) rearrangement reaction of allyl group to propenyl group”. In the obtained BPPN, X in the formula (1) is a hydrogen atom, and Y is a propenyl group.

Reference example 4
200 parts by mass of BPN-AE obtained in Reference Example 1 was charged into a reaction vessel, heated with stirring, and reacted at 200 ° C. for 2 hours, whereby partially allylated BPN-AE (hereinafter referred to as “BAPN-”). AE-5050 ") 199 parts by weight were obtained. The obtained BAPN-AE-5050 had a melt viscosity at 125 ° C. of 0.20 Pa · s. The above reaction corresponds to the aforementioned “d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)”. In the obtained BAPN-AE-5050, X and Y in the formula (1) are both partially hydrogen atoms and the other are allyl groups.

Example 1
240 parts by weight of BPN-AE obtained in Reference Example 1, 180 parts by weight of methanol, 60 parts by weight of isopropanol, 120 parts by weight of toluene, and 120 parts by weight of dimethyl sulfoxide were charged into a reaction vessel, heated, stirred and dissolved, and then marbled hydroxylated. 63 parts by mass of potassium was added and dissolved. The temperature was raised while distilling off methanol, isopropanol and toluene, and when the temperature reached 120 ° C., the system was switched to the reflux line and reacted at the same temperature for 20 hours. After completion of the reaction, 120 parts by mass of methanol, 240 parts by mass of toluene, and 120 parts by mass of water were added. After standing, the separated lower aqueous layer was removed, and then washing with water was repeated until the aqueous layer became neutral. Then, 228 parts by mass of propenylated BPN-AE (hereinafter referred to as “BPN-PE”) was obtained by distilling off toluene from the oil layer under heating and reduced pressure. The obtained BPN-PE had a melt viscosity at 125 ° C. of 0.08 Pa · s, and the proportion of propenyl groups in all alkenyl groups was 98%. The above reaction corresponds to the above-mentioned “c) rearrangement reaction of allyl ether form to propenyl ether form”. In the obtained BPN-PE, X in the formula (1) is a propenyl group, and Y is a hydrogen atom.

Example 2
The reaction vessel was charged with 227 parts by mass of BPPN, 590 parts by mass of epichlorohydrin, and 148 parts by mass of dimethyl sulfoxide obtained in Reference Example 3, and after heating, stirring, and dissolving, flaky sodium hydroxide 38. 7 parts by mass were added continuously over 1.5 hours. After completion of the addition of sodium hydroxide, the reaction was carried out at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Then, excess epichlorohydrin and dimethyl sulfoxide were distilled off under heating and reduced pressure, and 500 parts by mass of methyl isobutyl ketone was added to the residue to dissolve the residue. After removing by-product salts from this methyl isobutyl ketone solution by washing with water, 12 parts by mass of 30% aqueous sodium hydroxide solution is added and reacted at 70 ° C. for 1 hour, and then the washing of the reaction solution is washed with water. Repeat until. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 253 parts by mass of a propenyl group-containing epoxy resin (hereinafter referred to as “BPPN-GE”). The obtained BPPN-GE had an epoxy equivalent of 319 g / eq, a softening point of 74 ° C., a melt viscosity of 0.33 Pa · s at 150 ° C., and the proportion of propenyl groups in all alkenyl groups was 97%. The above reaction corresponds to the above-mentioned “b) glycidylation reaction of hydroxyl group in formula (2)”. In the obtained BPPN-GE, X in the formula (1) is a glycidyl group, and Y is a propenyl group.

Example 3
227 parts by mass of BPPN, 364 parts by mass of dimethyl sulfoxide, and 136 parts by mass of toluene obtained in Reference Example 3 were charged in a reaction vessel, heated with stirring and dissolved. Next, 48 parts by mass of flaky sodium hydroxide was added, and 91 parts by mass of allyl chloride was continuously added over 3 hours while maintaining the temperature at 40 ° C. After the addition of allyl chloride, the reaction was carried out at 45 ° C. for 1 hour and at 60 ° C. for 1 hour. Subsequently, dimethyl sulfoxide was distilled off under heating and reduced pressure, and 250 parts by mass of methyl isobutyl ketone was added to the residue to dissolve the residue. After adding water to this methyl isobutyl ketone solution and removing by-product salts by standing and liquid separation, washing with water was repeated until the waste liquid became neutral. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 240 parts by mass of BPPN allyl ether form (hereinafter referred to as “BPPN-AE”). The ratio of propenyl group in all alkenyl groups was 47%. The above reaction corresponds to the above-mentioned “a) hydroxylation reaction of hydroxyl group in the formula (2) (synthesis of allyl ether form)”. In the obtained BPPN-AE, X in the formula (1) is an allyl group, and Y is a propenyl group.
227 parts by mass of BPPN-AE obtained above, 364 parts by mass of dimethyl sulfoxide, and 136 parts by mass of toluene were charged into a reaction vessel, heated with stirring and dissolved. Next, 15 parts by mass of marble potassium hydroxide was added, the temperature was raised while distilling off toluene, and when the temperature reached 125 ° C., the system was switched to the reflux line and reacted at the same temperature for 20 hours. After completion of the reaction, 240 parts by mass of toluene and 100 parts by mass of water were added, and after standing, the separated lower aqueous layer was removed, and then washing with water was repeated until the aqueous layer became neutral. Subsequently, toluene was distilled off from the oil layer under heating and reduced pressure to obtain 220 parts by mass of BPPN-AE converted to propenyl ether (hereinafter referred to as “BPPN-PE”). The resulting BPPN-PE had a softening point of 84 ° C. and the proportion of propenyl groups in all alkenyl groups was 96%. The above reaction corresponds to the above-mentioned “c) rearrangement reaction of allyl ether form to propenyl ether form”. In the obtained BPPN-PE, X and Y in the formula (1) are propenyl groups.

Example 4
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 250 parts by mass of BAPN-AE-5050 obtained in Reference Example 4, 250 parts by mass of methanol, and 50 parts by mass of toluene. . Next, 90 parts by mass of marbled potassium hydroxide (purity 85%) was added, and the temperature was raised while distilling off methanol and toluene. When the temperature reached 100 ° C., the system was switched to the reflux line, and the reaction was carried out at the same temperature for 20 hours. went. After completion of the reaction, 50 parts by mass of methanol was added, and 143 parts by mass of concentrated hydrochloric acid was added for neutralization. 200 parts by mass of toluene was added, and after standing, the separated lower aqueous layer was removed, and then washing with water was repeated until the aqueous layer became neutral. Then, 242 parts by mass of propenylated BAPN-AE-5050 (hereinafter referred to as “BPPN-PE-5050”) was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The resulting BPPN-PE-5050 had a softening point of 52 ° C. and the proportion of propenyl groups in all alkenyl groups was 98%. The above reaction corresponds to the above-mentioned “e) rearrangement reaction of allyl group to propenyl group”. In the obtained BPPN-PE-5050, X and Y in the formula (1) are both partly hydrogen atoms and the others are propenyl groups.

Example 5
250 parts by mass of BPPN-PE-5050 obtained in Example 4, 590 parts by mass of epichlorohydrin, and 148 parts by mass of dimethyl sulfoxide were charged into a reaction vessel, heated, stirred, dissolved, and kept in a flaky shape while maintaining the temperature at 45 ° C. 20 parts by mass of sodium hydroxide was continuously added over 1.5 hours. After completion of the addition of sodium hydroxide, the reaction was carried out at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Then, excess epichlorohydrin and dimethyl sulfoxide were distilled off under heating and reduced pressure, and 500 parts by mass of methyl isobutyl ketone was added to the residue to dissolve the residue. After removing by-product salts from this methyl isobutyl ketone solution by washing with water, 6 parts by mass of 30% aqueous sodium hydroxide solution is added and reacted at 70 ° C. for 1 hour, and then the washing of the reaction solution is washed with water. Repeat until. Subsequently, 233 parts by mass of a propenyl group-containing epoxy resin (hereinafter referred to as “BPPN-GPE”) was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The epoxy equivalent of the obtained BPPN-GPE was 563 g / eq, the softening point was 58 ° C., the melt viscosity was 0.24 Pa · s at 150 ° C., and the proportion of propenyl groups in all alkenyl groups in the formula (1) was 98%. .
The above reaction corresponds to the above-mentioned “b) glycidylation reaction of hydroxyl group in formula (2)”. In the obtained BPPN-GPE, a part of X in the formula (1) is a glycidyl group, the other is a propenyl group, a part of Y is a hydrogen atom, and the other is a propenyl group.

Examples 6-9, Comparative Examples 1-3
The alkenyl group-containing resin, maleimide compound, and curing accelerator obtained in Reference Examples and Examples are blended in the proportions (parts by mass) shown in Table 1, and after heating and melt mixing, dicumyl peroxide is added to prepare the composition. After preparing, crushing, and tableting, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours. The results of measuring the physical properties of the cured product thus obtained for the following items are shown in Table 1.

-Heat resistance evaluation Glass transition temperature: Temperature measured by a dynamic viscoelasticity tester and tan δ is a maximum value.
Evaluation of thermal decomposability Td5 (5% thermal mass loss temperature): The obtained cured product was pulverized and powdered, and a 100 mesh pass, 200 mesh on sample was used to measure the thermal decomposition temperature by TG-DTA. The temperature at which the mass was reduced by 5% as measured with a sample amount of 10 mg, a heating rate of 10 ° C./min, and an air amount of 200 ml / hr.
-Hygroscopic evaluation Hygroscopicity: Mass increase rate after 24 hours at 85 ° C / 85% and 121 ° C / 100%. The test piece is a disk having a diameter of 50 mm and a thickness of 4 mm.

note)
BMI: 4,4′-bismaleimide diphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
DCPO: Dicumyl peroxide (manufactured by Kayaku Akzo)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

From Table 1, the cured product of the epoxy resin composition using the alkenyl group-containing resin of the present invention is a comparative example 1 (wherein X is an allyl group and Y is a hydrogen atom in BPN allyl ether form formula (1)), comparison Example 2 (Allylated BPN Formula (1) Y is an allyl group and X is a hydrogen atom), Comparative Example 3 (Propenylated BPN Formula (1) Y is a propenyl group and X is a hydrogen atom) As compared with the cured product, it can be confirmed that excellent low moisture absorption (low water absorption) and high heat resistance (solder reflow resistance) are exhibited.
Therefore, the alkenyl group-containing resin of the present invention includes an insulating material for electrical and electronic parts (high reliability semiconductor encapsulating material, etc.), a laminated board (printed wiring board, a substrate for BGA, a buildup board, etc.), an adhesive (conductive) This is useful for various composite materials such as adhesives, CFRP, and paints.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2016-250404) filed on Dec. 26, 2016, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims

An alkenyl group-containing resin represented by the following formula (1), wherein 20% or more of a plurality of alkenyl groups in X and Y are propenyl groups.

(Wherein a plurality of Z's each independently represents a hydrocarbon group having 6 to 15 carbon atoms. A plurality of X's each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, propenyl) Represents a group or a glycidyl group, except for the case where all of a plurality of X are hydrogen atoms or allyl groups, each of the plurality of Y independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or Represents a propenyl group, n represents the number of repetitions, and the average value is a real number of 1 to 20.)
The alkenyl group-containing resin according to claim 1, wherein a plurality of Xs in the formula (1) represent an allyl group, a propenyl group, or a glycidyl group, and all Xs are not allyl groups.
The alkenyl group-containing resin according to claim 1 or 2, wherein 20% or more of the plurality of Xs in the formula (1) are alkenyl groups.
The alkenyl group-containing resin according to any one of claims 1 to 3, wherein Z in the formula (1) is an aromatic-containing hydrocarbon group.
The alkenyl group-containing resin according to any one of claims 1 to 4, wherein Z in the formula (1) is a hydrocarbon group having 10 to 15 carbon atoms.
A curable resin composition containing the alkenyl group-containing resin according to any one of claims 1 to 5.
The curable resin composition according to claim 6 containing a radical polymerization initiator.
The curable resin composition according to claim 6 or 7, comprising a maleimide compound.
A cured product obtained by curing the curable resin composition according to any one of claims 6 to 8.