JP6963565B2 - Alkenyl group-containing resin, curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to an alkenyl group-containing resin, a curable resin composition, and a cured product thereof. It is suitably used for electrical and electronic parts such as build-up laminates and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

In recent years, the required characteristics of laminated boards on which electrical and electronic components are mounted have become widespread and sophisticated due to the expansion of their fields of use. For example, in the past, semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing capacity such as central processing units (hereinafter referred to as "CPU") are made of polymer materials. It is often mounted on the laminated board to be made. As the processing speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become problems, and low dielectric constants and low dielectric loss tangents are required for wiring boards. There is. At the same time, as the processing speed of the element 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 have come to be used and carried in outdoor environments and in the immediate vicinity of the human body. Resistance is required.
Furthermore, in the automobile field, computerization is progressing, and precision electronic devices may be placed near the engine, so heat resistance and moisture resistance are required at a higher level, and trains, air conditioners, etc. SiC semiconductors have begun to be used in the above, and high heat resistance is required for the encapsulant of the semiconductor element, and the conventional epoxy resin encapsulant cannot cope with it.
In recent years, the weight of airplanes, automobiles, trains, ships, etc. has been reduced due to the need for energy saving. In the field of vehicles, studies have been made especially on replacing what used to be a metal material with a lightweight and high-strength carbon fiber composite material. For example, in the Boeing 787, the weight is reduced by increasing the ratio of the composite material, and the fuel efficiency is greatly improved. In the automobile field, it is equipped with a shaft made of composite material, although it is a part, and there is also a movement to make the car body from composite material for luxury cars. In response to these demands, many proposals have been made mainly for epoxy resins and resin compositions containing them. (Patent Document 3, Patent Document 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 completely substituted with an allyl group.

Japanese Patent Application Laid-Open No. 04-359911 International Publication 2016/002704 Japanese Patent Application Laid-Open No. 2009-001783 Japanese Patent Application Laid-Open No. 01-294662

However, since Patent Document 1 uses a phenol resin substituted with a propenyl group, it has poor hygroscopicity, and accordingly, its electrical characteristics are insufficient. Further, since Patent Document 2 uses a phenol resin substituted with an allyl group, the reactivity is poor and the hygroscopicity is poor, and the performance is not yet 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, which exhibit excellent low hygroscopicity (low water absorption) and heat resistance in the cured product.

As a result of diligent research 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) in which 20% or more of the alkenyl groups in a plurality of X and Y are propenyl groups.

(In the formula, each of the plurality of Zs independently represents a hydrocarbon group having 6 to 15 carbon atoms. The plurality of Xs independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, and propenyl. Represents a group or glycidyl group, except when all of the plurality of Xs are hydrogen atoms or allyl groups. The plurality of Ys are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, allyl groups or allyl groups. It 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 the preceding item [1], wherein a plurality of Xs present in the formula (1) are allyl groups, propenyl groups or glycidyl groups, and not all Xs are allyl groups.
[3] The alkenyl group-containing resin according to the preceding item [1] or [2], wherein 20% or more of the plurality of Xs present in the formula (1) are alkenyl groups.
[4] The alkenyl group-containing resin according to any one of the above items [1] to [3], wherein Z is an aromatic-containing hydrocarbon group in the above formula (1).
[5] The alkenyl group-containing resin according to any one of the above items [1] to [4], wherein Z is a hydrocarbon group having 10 to 15 carbon atoms in the above formula (1).
[6] A curable resin composition containing the alkenyl group-containing resin according to any one of the preceding items [1] to [5].
[7] The curable resin composition according to the previous item [6], which contains a radical polymerization initiator.
[8] The curable resin composition according to the above item [6] or [7], which contains a maleimide compound.
[9] A cured product obtained by curing the curable resin composition according to any one of the preceding items [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 hygroscopicity (low water absorption) and heat resistance (solder reflow resistance). Therefore, insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulation materials, etc.), laminated boards (printed wiring boards, BGA substrates, build-up substrates, etc.), liquid crystal encapsulants, EL encapsulants, adhesives (conductive) It can be used for various composite materials such as (sex adhesives, etc.) and CFRP, and for paints and the like.

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).

(In the formula, each of the plurality of Zs independently represents a hydrocarbon group having 6 to 15 carbon atoms. The plurality of Xs independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, and propenyl. Represents a group or glycidyl group, except when all of the plurality of Xs are hydrogen atoms or allyl groups. The plurality of Ys are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, allyl groups or allyl groups. It 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, some or all of the allyl groups are converted into more reactive propenyl groups, and as a result, the propenyl groups react with each other in the curing process, so that the crosslink density increases. Heat resistance (glass transition temperature) is improved. On the other hand, even when mixed with a reactive olefin resin such as a maleimide group or an acrylate group, the propenyl group is easier to react than the allyl group. Further, unlike the reaction of epoxy groups, polar groups are not generated, so that the increase in water absorption (wetness) due to the improvement of heat resistance is small.

In the alkenyl group-containing resin of the present invention, in the above formula (1), X is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group (-CH ₂ -CH = CH ₂ ), and a propenyl group (-CH 2-CH = CH 2). -CH = CH-CH ₃ ) or glycidyl group, where Y is an independent 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 20% or more of all alkenyl groups (that is, the total of allyl group and propenyl group) is a propenyl group, more preferably 40% or more, from the viewpoint of heat resistance and hygroscopicity. 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 the plurality of X existing in the formula (1) are hydrogen atoms or allyl groups is excluded. For example, in the case of a compound in which all of the plurality of Xs present in the above formula (1) are hydrogen atoms and all of the plurality of Ys present are propenyl groups, the hydroxyl group remains as it is in the cured product or is reacted with the epoxy. Since an alcoholic hydroxyl group is generated, the hygroscopic property is high, and there is a risk that the electrical characteristics may be deteriorated accordingly.
Further, in the case of an allyl ether-modified biphenyl aralkylnovolac resin in which all of the plurality of Xs present in the above formula (1) are allyl groups and all the plurality of Ys are hydrogen atoms, the allyl ether groups are highly reactive. There is a risk of slow curing and poor productivity. In addition, since high temperature is required for curing, the allyl ether group may be rearranged during curing to generate hydroxyl groups, which may adversely affect low hygroscopicity.
Further, in the case of a compound in which all of the plurality of Xs present in the above formula (1) are hydrogen atoms and all of the plurality of Ys present are allyl groups, the allyl groups have poor reactivity, so that curing is delayed and production is carried out. There is a risk of poor sex. Further, since the hydroxyl group remains as it is in the cured product or is reacted with the epoxy to generate an alcoholic hydroxyl group, the hygroscopicity is high, and there is a risk that 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 the plurality of X and Y are propenyl groups, even if a part of the plurality of X and Y is an alkyl group having 1 to 6 carbon atoms. good. Examples of the alkoxy group having 1 to 6 carbon atoms include an alkyl group having a linear, branched or cyclic structure such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

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

Further, in the above equation (1), the average value of n is 1 to 20, preferably 1 to 10, and particularly preferably 1 to 6.

In the above 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. Is preferable, and more preferably 210 to 3000 g / eq. Is. Epoxy equivalent is 5000 g / eq. The following indicates that the amount of epoxy groups per unit structure does not decrease, and 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 method for producing the alkenyl group-containing resin of the present invention will be described.
First, the alkenyl group-containing resin of the present invention uses the phenol resin of the following formula (2) as a raw material.

(In the formula, each of the plurality of Zs independently represents a hydrocarbon group having 6 to 15 carbon atoms. The plurality of Ys independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group or propenyl, respectively. Represents a group. 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) Hydroxyl group allylation reaction in formula (2) (synthesis of allyl ether)
b) Glycidylation reaction of hydroxyl group in formula (2) c) Rearrangement reaction of allyl ether to propenyl ether d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenolic resin)
e) Rearrangement reaction of allyl group to propenyl group

Hereinafter, each reaction step will be described in detail.
a) Hydroxy hydroxyl allylation reaction (synthesis of allyl ether)
The reaction of allylating (allyl etherifying) the hydroxyl group of the phenol resin represented by the above formula (2) can be carried out by a known method, and generally allyl chloride or allyl chloride is used using a base such as an alkali metal hydroxide. Allyl halides such as allyl bromide and allyl iodide are reacted to form allyl ether.
At this time, highly polar solvents such as methanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrolidone are 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. Further, these may be used alone or in combination, or may be used in combination with a solvent having a low polarity such as toluene or xylene.
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, and the allyl group is added by adjusting the amount used. The rate can be adjusted.
For example, more specifically, after dissolving the phenol resin in the above-mentioned isopropanol or dimethyl sulfoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to prepare the alkali metal hydroxide at 50 to 100 ° C. After dissolution, allyl chloride or allyl bromide is added at 30-50 ° C. for 2-5 hours, followed by reaction at 30-70 ° C. for 1-10 hours. After completion of the reaction, toluene, methyl isobutyl ketone, etc. are added, the by-produced salt is removed by filtration, washing with water, etc., and a solvent such as toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure to obtain an allyl ether body. Can be done.

b) Glysidylation of hydroxyl groups in formula (2) (synthesis of epoxy resin)
The reaction of glycidylating the hydroxyl group of the phenol resin in the formula (2) is a known method, and generally, epichlorohydrin, epibromhydrin, epiiodohydrin, etc. are used using a base such as an alkali metal hydroxide. Epihalohydrin is reacted to form glycidyl ether.
For example, a mixture of phenol formaldehyde and epihalohydrins is reacted at 20 to 120 ° C. for 1 to 20 hours while adding solid alkali metal hydroxides such as sodium hydroxide and potassium hydroxide all at once or gradually. At this time, an aqueous solution may be used as the alkali metal hydroxide. In that case, the alkali metal hydroxide is continuously added and water and epihalohydrins are continuously added from the reaction system under reduced pressure or under normal pressure. The epihalohydrins may be continuously returned to the reaction system by distilling off the liquid and further separating the liquid to remove the water.
In the above method, the amount of epihalohydrins used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, based on 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, based on 1 equivalent of the hydroxyl group of the phenol resin.
Further, in the above reaction, by adding an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide (DMSO), dimethylformamide, 1,3-dimethyl-2-imidazolidinone, an epoxy resin having a low hydrolyzable halogen concentration can be obtained. 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 epihalohydrins. In addition to the above solvent, the reaction can be facilitated by adding alcohols such as methanol and ethanol. Further, toluene, xylene, dioxane and the like can also be used.
Usually, these reactants are washed with water or after removing excess epihalohydrins under heating and reduced pressure without washing with water, and then dissolved in a solvent such as toluene, xylene, methylisobutylketone, etc., and sodium hydroxide, potassium hydroxide, etc. An aqueous solution of alkali metal hydroxide is added and the reaction is carried out again. 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, based on 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, or the like, and a solvent such as toluene, xylene, or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy resin having a small amount of hydrolyzable halogen.

c) Rearrangement reaction of allyl ether 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 reacted with a strong base in a polar solvent. Examples of the polar solvent used include, but are not limited to, methanol, isopropanol, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Ketone-based 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 mass, preferably 50 to 300 parts by mass with respect to 100 parts by mass of the raw material, and these may be used alone or in combination, and toluene, xylene and the like may be used. A solvent may be used in combination. Examples of the strong base 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 the strong base used varies greatly depending on the type of solvent used, the type of base, etc., but is usually 0.1 to 3.0 mol, preferably 0.2 to 2. It is in the range of 0 mol.
For example, more specifically, a compound having an allyl ether group is dissolved in dimethyl sulfoxide or 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. under heating and reduced pressure to obtain the propenyl ether body. Obtainable. The conversion rate to the propenyl ether group can also be adjusted by adjusting the type and amount of the strong base, the reaction temperature, and the reaction time.

d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)
The Kreisen transition reaction may be carried out according to a conventional method. For example, a compound having an allyl ether group may be mixed at 150 to 230 ° C. in the presence of a high boiling point solvent such as carbitol, paraffin oil, N, N'-dimethylaniline or in the absence of a solvent. Heat for 0.5 to 100 hours. The solvent is used as needed in an amount of 10 to 200 parts by mass with respect to 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, it is preferable to carry out the reaction in vacuum or in an atmosphere of an inert gas such as nitrogen or argon, and coloring of the product can be prevented. However, it is difficult to maintain a complete vacuum or an atmosphere of an inert gas, and it is inevitable that a small amount of oxygen is mixed into the system. Therefore, it is preferable to add an antioxidant to carry out the Claisen rearrangement. It is preferable to use about 10 parts by mass of the antioxidant with respect to 100 parts by mass of allyl ether. Examples of phenolic antioxidants include methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tert-butylated bisphenol A, and 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) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-) Examples thereof include, but are not limited to, 4-hydroxybenzyl) benzene and 1,1-bis (4-hydroxyphenyl) -cyclohexane. Further, 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 propenyl groups can also be adjusted by adjusting the reaction temperature and reaction time.

e) Rearrangement reaction of allyl group to propenyl group The rearrangement reaction of allyl group to propenyl group can be carried out by a known method, and is generally reacted with a strong base in a polar solvent. Examples of the polar solvent used include, but are not limited to, methanol, isopropanol, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and the like. Ketone-based 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 mass, preferably 50 to 300 parts by mass with respect to 100 parts by mass of the raw material, and these may be used alone or in combination, and toluene, xylene and the like may be used. A solvent may be used in combination. Examples of the strong base 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 the strong base used varies greatly depending on the type of solvent used, the type of base, etc., but is usually 0.1 to 3.0 mol, preferably 0.2 to 2. It is in the range of 0 mol.
For example, more specifically, after dissolving a compound having an allyl group in methanol, dimethyl sulfoxide, etc., sodium hydroxide and potassium hydroxide are added, and the mixture is reacted at 50 to 150 ° C. for 2 to 10 hours. After completion of the reaction, the compound has a propenyl group by neutralizing, adding toluene, methyl isobutyl ketone, etc., removing the neutralizing salt by washing with water, and distilling off a solvent such as toluene, methyl isobutyl ketone, etc. under heating and reduced pressure. Can be obtained. The conversion rate to propenyl ether groups 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).

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

The curable resin composition of the present invention may contain the alkenyl group-containing resin of the present invention, and may 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.
As the maleimide compound that can be blended in the curable resin composition of the present invention, a conventionally known maleimide compound can be used. Specific examples of the maleimide compound include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis [4- (4-maleimidephenoxy) phenyl] propane, 3,3. '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulphon bismaleimide , 1,3-Bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) 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 in the range of 5 times or less, more preferably 2 times or less in terms of mass ratio.
Further, the maleimide compounds described in Japanese Patent Application Laid-Open No. 2009-001783 (Patent Document 3) and Japanese Patent Application Laid-Open No. 01-294662 (Patent Document 4) have low moisture absorption, flame retardancy, and dielectric. It is particularly preferable as a maleimide compound because of its excellent properties.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator to react the alkenyl groups of the alkenyl group-containing resin of the present invention with each other or the alkenyl group with the 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. Known curing accelerators of azo compounds can be mentioned, but the present invention is not particularly limited thereto. 0.01 to 5 parts by mass is preferable, and 0.01 to 3 parts by mass is particularly preferable with respect to 100 parts by mass by mass of the curable resin composition.

The curable resin composition of the present invention may contain an epoxy resin. As the 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, polycondensations of phenols and ketones, and polycondensates of bisphenols and various aldehydes. Alicyclic epoxies typified by glycidyl ether-based epoxy resins obtained by glycidylizing alcohols, 4-vinyl-1-cyclohexene epoxides, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, etc. Examples thereof include, but are not limited to, resins, glycidylamine-based epoxy resins typified by tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester-based epoxy resins. These may be used alone or in combination of two or more.
Further, the epoxy resin obtained by subjecting a phenol aralkyl resin obtained by a condensation reaction of phenols with the above-mentioned bishalogenomethyl aralkyl derivative or aralkyl alcohol derivative as a raw material and subjecting it to a dehydroxylation reaction with epichlorohydrin has low moisture absorption. It is particularly preferable as an epoxy resin because it has excellent flame retardancy and dielectric properties.

When the curable resin composition of the present invention contains an epoxy resin, a catalyst for curing the epoxy resin (curing accelerator) can be blended if 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 blending amount of the curing catalyst is preferably in the range of 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the 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 a preferred embodiment thereof.
As the epoxy resin curing agent, an amine compound, an acid anhydride compound, an amide compound, a phenol compound and the like can be used. Specific examples of the curing agent that can be used include a polyamide resin synthesized from a dimer of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and linolenic acid and ethylenediamine, phthalic anhydride, and trihydride anhydride. Merit acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substitution) Phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, polycondensates of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylols, 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, relative to 1 equivalent of the epoxy group (or glycidyl group). When the amount is 0.5 equivalents or more or 1.5 equivalents or less with respect to 1 equivalent of the epoxy group, the curing becomes more reliable and better cured physical properties can be obtained.

The curable resin composition of the present invention may contain a cyanate ester resin. As the cyanate ester compound that can be blended in the curable resin composition of the present invention, a conventionally known cyanate ester compound can be used. Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensations of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Examples thereof include cyanate ester compounds obtained by reacting a substance with cyanide halide, but the present invention is not limited thereto. 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, alkylaldehyde, 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, benzophenone and the like.
Specific examples of the cyanate ester compound include dicyanatobenzene, tricyanatebenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis (4-cyanatophenyl) propane, and bis (4-cyanatophenyl). ) Methan, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2'-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2'-bis (4-shear) Nart phenyl) ethane, 2,2'-bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether, phenol novolac cyanato, phenol di Examples thereof include those obtained by converting the hydroxyl group of the cyclopentadiene cocondensate into a cyanate group, but the present invention is not limited thereto.
Further, the cyanate ester compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferable as the cyanate ester compound because it is excellent in low hygroscopicity, flame retardancy and dielectric properties.

When the curable resin composition of the present invention contains a cyanate resin, zinc naphthenate, cobalt naphthenate, copper naphthenate, etc. Catalysts such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, and dibutyltin maleate can also be included. The catalyst is usually 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the thermosetting resin composition.

Further, the curable resin composition of the present invention contains, if necessary, molten silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia. , Aluminum nitride, graphite, forsterite, steatite, spinel, mulite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or an inorganic filler obtained by spheroidizing or crushing these powders. Can be done. Further, particularly when a curable resin composition for encapsulating a semiconductor is obtained, the amount of the above-mentioned 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. be.

A known additive can be added to the curable resin composition of the present invention, if necessary. Specific examples of the additives that can be used include fillings such as polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimides, fluororesins, silicone gels, silicone oils, and silane coupling agents. Examples thereof include surface treatment agents for materials, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The blending amount of these additives is preferably in the range of 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 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 pre-cured at 130 to 180 ° C. for 30 to 500 seconds, and further, 150 to 200 ° C. After curing for 2 to 15 hours, a sufficient curing reaction proceeds, and the cured product of the present invention is obtained. It is also possible to uniformly disperse or dissolve the components of the curable resin composition in a solvent or the like, remove the solvent, and then cure.

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 where moisture resistance, heat resistance, and high adhesiveness are required. Specifically, it is useful as a material for all electrical and electronic parts such as an insulating material, a laminated board (printed wiring board, BGA board, build-up board, etc.), a sealing material, and a resist. In addition to molding materials and composite materials, it can also be used in fields such as paint materials and adhesives. Especially 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. Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), STOP (thin small outline package), and TQFP. (Syncwad flat package) and the like.

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 γ-butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone and other amide solvents, tetramethylene sulfone and the like. Ethereal solvents such as sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Examples include solvents and aromatic solvents such as toluene and xylene. The solvent is used in a range in which the solid content concentration of the obtained varnish excluding the solvent 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 uniformly mixed 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, a maleimide resin, and if necessary, an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives may be added to prepolymerize. In the absence of a solvent, for example, an extruder, a kneader, a roll, or the like is used for mixing or prepolymerizing each component, and in the presence of a solvent, a reaction kettle with a stirrer or the like is used.

A prepreg can be obtained by heating and melting the curable resin composition of the present invention, lowering the viscosity, and impregnating reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
A prepreg can also be obtained by impregnating the reinforcing fibers with the varnish and heating and drying the varnish.
The above prepreg is cut into a desired shape, laminated with copper foil or the like if necessary, and then the curable resin composition is heat-cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. This makes it possible to obtain a laminated board (printed wiring board) for electrical and electronic use and a carbon fiber reinforcing material.

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, the epoxy equivalent, the melt viscosity, the softening point, and the total chlorine concentration were measured under the following conditions.
Epoxy equivalent: Measured according to JIS K-7236.
Melt viscosity: Melt viscosity in the cone plate method.
Softening point: Measured according to JIS K-7234.
Percentage of propenyl groups in all alkenyl groups: measured by NMR.
Total chlorine: Automatic sample combustion-ion chromatograph device AQF-2100H type Mitsubishi Chemical Corporation Argon gas flow rate is 200 ml / min and oxygen gas flow rate is 400 ml / min. After combustion decomposition, ion content is measured.

Reference example 1
A phenol resin represented by the following formula (3) (hereinafter referred to as "BPN"; softening point 74 ° C., melt viscosity 0.16, hydroxyl group equivalent 210 g / eq) is placed in a flask equipped with a thermometer, a cooling tube, 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 charged, and after heating, stirring and melting, 102 parts by mass of allyl chloride was added while maintaining the temperature at 40 ° C. It was added continuously over time. After the addition of allyl chloride was completed, the reaction was carried out at 45 ° C. for 1 hour and at 60 ° C. for 1 hour. Then, 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. Water was added to this methyl isobutyl ketone solution, and the by-product salt was removed by allowing it to stand and separating the solution, and then washing with water was repeated until the waste liquid became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 243 parts by mass of an allyl etheric body of BPN (hereinafter referred to as "BPN-AE"). The above reaction corresponds to the above-mentioned "a) hydroxyl group allylation reaction (synthesis of allyl ether form) in the formula (2). Further, 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 from 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 to allylate BPN (hereinafter referred to as “BAPN”) 199. A mass portion was obtained. The above reaction corresponds to the above-mentioned "d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)". Further, in the obtained BAPN, X in the formula (1) is a hydrogen atom and Y is an allyl group.

Reference example 3
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 227 parts by mass of BAPN, 227 parts by mass of methanol, and 35 parts by mass of toluene obtained in Reference Example 2 were charged, heated with stirring, and dissolved. Next, 90 parts by mass of marbled potassium hydroxide (purity 85%) was added, the temperature was raised while distilling off methanol and toluene, and when the temperature reached 100 ° C., the reaction was switched to a 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, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 228 parts by mass of propenylated BPN (hereinafter referred to as “BPPN”). The above reaction corresponds to the above-mentioned "e) rearrangement reaction of an allyl group to a propenyl group". Further, 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 to partially allylate BPN-AE (hereinafter, “BAPN-”). It is expressed as "AE-5050".) 199 parts by mass was obtained. The melt viscosity of the obtained BAPN-AE-5050 at 125 ° C. was 0.20 Pa · s. The above reaction corresponds to the above-mentioned "d) Claisen rearrangement reaction of allyl ether (synthesis of allylated phenol resin)". Further, in the obtained BAPN-AE-5050, X and Y in the formula (1) are all hydrogen atoms in part and allyl groups in others.

Example 1
240 parts by mass of BPN-AE, 180 parts by mass of methanol, 60 parts by mass of isopropanol, 120 parts by mass of toluene, and 120 parts by mass of dimethylsulfoxide obtained in Reference Example 1 were charged into a reaction vessel, heated, stirred, and dissolved, and then marbled hydroxide. 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 reaction was switched to a reflux line and the reaction was carried out 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, and after standing, the separated lower aqueous layer was removed, and then washing with water was repeated until the aqueous layer became neutral. Then, toluene was distilled off from the oil layer under heating and reduced pressure to obtain 228 parts by mass of propenylated BPN-AE (hereinafter referred to as "BPN-PE"). The melt viscosity of the obtained BPN-PE at 125 ° C. was 0.08 Pa · s, and the proportion of propenyl groups in the total alkenyl groups was 98%. The above reaction corresponds to the above-mentioned "c) Rearrangement reaction of allyl ether to propenyl ether". Further, in the obtained BPN-PE, X in the formula (1) is a propenyl group and Y is a hydrogen atom.

Example 2
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 were charged into a reaction vessel, and after heating, stirring, and dissolution, the temperature was maintained at 45 ° C., and flaky sodium hydroxide 38. 7 parts by mass was added continuously over 1.5 hours. After the addition of sodium hydroxide was completed, 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 the by-product salt from this methyl isobutyl ketone solution by washing with water, 12 parts by mass of a 30% aqueous sodium hydroxide solution is added, and the mixture is reacted at 70 ° C. for 1 hour, and then the reaction solution is washed with water to make the washing solution neutral. Repeated until. Then, 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 epoxy equivalent of the obtained BPPN-GE was 319 g / eq, the melt viscosity at a softening point of 74 ° C. and 150 ° C. was 0.33 Pa · s, and the proportion of propenyl groups in the total alkenyl groups was 97%. The above reaction corresponds to the above-mentioned "glycidylation reaction of hydroxyl groups in the above-mentioned formula (2)". Further, 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 into 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 was completed, the reaction was carried out at 45 ° C. for 1 hour and at 60 ° C. for 1 hour. Then, 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. Water was added to this methyl isobutyl ketone solution, and the by-product salt was removed by allowing it to stand and separating the solution, and then washing with water was repeated until the waste liquid became neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 240 parts by mass of an allyl ether of BPPN (hereinafter referred to as "BPPN-AE"). The proportion of propenyl groups in all alkenyl groups was 47%. The above reaction corresponds to the above-mentioned "a) hydroxyl group allylation reaction (synthesis of allyl ether form) in the formula (2). Further, 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, 364 parts by mass of dimethyl sulfoxide, and 136 parts by mass of toluene obtained above were charged into a reaction vessel, heated with stirring, and dissolved. Next, 15 parts by mass of marbled potassium hydroxide was added, the temperature was raised while distilling off toluene, the temperature was switched to a reflux line when the temperature reached 125 ° C., and the reaction was carried out 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. Then, toluene was distilled off from the oil layer under heating and reduced pressure to obtain 220 parts by mass of propenyl etherified BPPN-AE (hereinafter referred to as "BPPN-PE"). The softening point of the obtained BPPN-PE was 84 ° C., and the proportion of propenyl groups in the total alkenyl groups was 96%. The above reaction corresponds to the above-mentioned "c) Rearrangement reaction of allyl ether to propenyl ether". Further, in the obtained BPPN-PE, X and Y in the formula (1) are propenyl groups.

Example 4
In a flask equipped with a thermometer, a cooling tube, and a stirrer, 250 parts by mass of BAPN-AE-5050, 250 parts by mass of methanol, and 50 parts by mass of toluene obtained in Reference Example 4 were charged, heated with stirring, and dissolved. .. Next, 90 parts by mass of marbled potassium hydroxide (purity 85%) was added, the temperature was raised while distilling off methanol and toluene, and when the temperature reached 100 ° C., the reaction was switched to a 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, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 242 parts by mass of propenylated BAPN-AE-5050 (hereinafter referred to as "BPPN-PE-5050"). The softening point of the obtained BPPN-PE-5050 was 52 ° C., and the proportion of propenyl groups in the total alkenyl groups was 98%. The above reaction corresponds to the above-mentioned "e) rearrangement reaction of an allyl group to a propenyl group". Further, in the obtained BPPN-PE-5050, X and Y in the formula (1) are all hydrogen atoms and the others are propenyl groups.

Example 5
250 parts by mass of BPPN-PE-5050, 590 parts by mass of epichlorohydrin, and 148 parts by mass of dimethyl sulfoxide obtained in Example 4 were charged into a reaction vessel, heated, stirred, and melted, and then flaked while maintaining the temperature at 45 ° C. 20 parts by mass of sodium hydroxide was continuously added over 1.5 hours. After the addition of sodium hydroxide was completed, 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 the by-product salt from this methyl isobutyl ketone solution by washing with water, 6 parts by mass of a 30% aqueous sodium hydroxide solution is added, and the mixture is reacted at 70 ° C. for 1 hour, and then the reaction solution is washed with water to make the washing solution neutral. Repeated until. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 233 parts by mass of a propenyl group-containing epoxy resin (hereinafter referred to as “BPPN-GPE”). The epoxy equivalent of the obtained BPPN-GPE was 563 g / eq, the melt viscosity at a softening point of 58 ° C. and 150 ° C. was 0.24 Pa · s, and the proportion of propenyl groups in the total alkenyl groups in the formula (1) was 98%. ..
The above reaction corresponds to the above-mentioned "glycidylation reaction of hydroxyl groups in the above-mentioned formula (2)". Further, 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, heated and melt-mixed, and then dicumyl peroxide is added to prepare the composition. After preparation, crushing and tableting, a resin molded product was prepared by transfer molding and cured at 200 ° C. for 2 hours. Table 1 shows the results of measuring the physical characteristics of the cured product thus obtained for the following items.

-Heat resistance evaluation Glass transition temperature: The temperature when tan δ is the maximum value measured by a dynamic viscoelasticity tester.
-Evaluation of thermal decomposition Td5 (5% thermal mass reduction temperature): The thermal decomposition temperature was measured by TG-DTA using a sample of 100 mesh pass and 200 mesh on of the obtained cured product crushed into powder. The temperature at which the mass was reduced by 5% as measured at 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 with a diameter of 50 mm and a thickness of 4 mm.

note)
BMI: 4,4'-bismaleimidediphenylmethane (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 was compared with Comparative Example 1 (X is an allyl group and Y is a hydrogen atom in the allyl ether form (1) of BPN). In Example 2 (in the allylated BPN formula (1) Y is an allylic group and X is a hydrogen atom), in Comparative Example 3 (in the propenylated BPN formula (1) Y is a propenyl group and X is a hydrogen atom). It can be confirmed that it exhibits excellent low moisture absorption (low water absorption) and high heat resistance (solder reflow resistance) as compared with the cured product.
Therefore, the alkenyl group-containing resin of the present invention is an insulating material for electrical and electronic parts (highly reliable semiconductor encapsulation material, etc.), a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), and an adhesive (conductive). It is useful for various composite materials such as adhesives) and CFRP, and for paints.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications 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 December 26, 2016, and the entire application is incorporated by reference. Also, all references cited here are taken in as a whole.

Claims (7)

An alkenyl group-containing resin represented by the following formula (1), wherein 50 % or more of the alkenyl groups in a plurality of X and Y are propenyl groups (-CH = CH-CH _3).

(In the formula, a plurality of Zs present independently represent one or more types selected from the following structures.

A plurality of Xs independently represent 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. .. However, this excludes the case where all of the plurality of Xs are hydrogen atoms or allyl groups (-CH ₂ -CH = CH _2). A plurality of Ys independently represent 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 ). n represents the number of repetitions, and the average value is a real number of 1 to 20. ) In the formula (1), a plurality of Xs present represent an allyl group (-CH ₂ -CH = CH ₂ ), a propenyl group (-CH = CH-CH ₃ ) or a glycidyl group, and all Xs represent an allyl group (-CH). ₂ -CH = CH ₂₎ alkenyl group-containing resin according to claim 1 is not be. The alkenyl group-containing resin according to claim 1 or 2, wherein 20% or more of the plurality of Xs present in the formula (1) are alkenyl groups. A curable resin composition containing the alkenyl group-containing resin according to any one of claims 1 to 3. The curable resin composition according to claim 4 , which contains a radical polymerization initiator. The curable resin composition according to claim 4 or 5 , which contains a maleimide compound. A cured product obtained by curing the curable resin composition according to any one of claims 4 to 6.