JP7153994B2 - Alkenyl group-containing compound, curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to an alkenyl group-containing compound, a curable resin composition and a cured product thereof, and includes 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 electric/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, due to the expansion of the fields of application of laminates on which electrical and electronic components are mounted, the required properties are becoming more extensive and sophisticated. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are stacked layers made of polymer materials. It is becoming more and more common to be mounted on a board. As the processing speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become problems. It is In addition, as the processing speed of elements increases, the heat generation of the chip increases, and therefore, the improvement of heat resistance is required at the same time.

In particular, as semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like become smaller, thinner, and more dense, there is a demand for thinner PKG substrates. As a result, problems such as large warping occur due to heating during solder mounting of the PKG to the motherboard (PCB). In order to reduce this, a PKG substrate material with a high Tg (for example, 260° C. or higher, recently 288° C. or higher) higher than the solder mounting temperature is required.

On the other hand, the frequency of electrical signals handled by information and communication equipment tends to increase year by year due to the recent trend toward large-capacity, high-speed communications. Therefore, transmission loss increases and it becomes difficult to transmit signals efficiently. In order to reduce this, a substrate material with a low dielectric loss tangent is also sought.

Especially in the 5th generation communication system "5G", which is currently being developed, it is expected that further increase in capacity and high speed communication will progress in data communication of various devices including smartphones. The need for low dielectric loss tangent materials is increasing more and more, and a dielectric loss tangent of 0.005 or less at least at 1 GHz is required, and materials that can achieve this heat resistance and dielectric properties (dielectric loss tangent) are required. Furthermore, in the automotive field, the use of electronics is progressing, and precision electronic equipment is sometimes placed near the engine driving part, so a higher level of heat resistance and moisture resistance is required. In addition, SiC semiconductors have begun to be used in trains, air conditioners, and the like, and extremely high heat resistance is required for the sealing material for semiconductor elements.

However, since Patent Document 1 uses phenolic resins substituted with propenyl groups, the electrical properties are insufficient. Further, in Patent Document 2, since a phenolic resin substituted with allyl groups is used, the reactivity is poor, and it is difficult to say that the performance is satisfactory from the viewpoint of heat resistance. Development of curing systems is desired.

Japanese Patent Laid-Open No. 04-359911 WO2016/002704

The present invention has been made in view of such circumstances, and provides an alkenyl group-containing compound and a curable resin composition that exhibit excellent heat resistance and electrical properties when cured, and a cured product thereof. With the goal.

The inventors of the present invention have made a sincere study to solve the above problems, and as a result, found that the use of a specific alkenyl group-containing compound makes the cured product excellent in heat resistance and electrical properties, and have completed the present invention. rice field.
That is, the present invention relates to the following [1] to [6].
[1]
An alkenyl group-containing compound represented by the following formula (1).

(In formula (1), X represents an arbitrary organic group. Y represents an alkenyl group. When there are multiple Y, they may be the same or different. Z is independently a hydrogen atom. , represents a hydrocarbon group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms, and when there are multiple Zs, they may be the same or different l is a natural number of 1 to 6 represents m and n are each an integer of 0 or more, satisfies m + n = 1 to 5, and at least one of l m is 1 or more.)
[2]
The alkenyl group-containing compound according to [1] above, wherein X in formula (1) contains any one of structures represented by the following formulas (2-1) to (2-4).

(In formulas (2-1) to (2-4), * represents a bond to the oxygen atom of formula (1).)
[3]
The alkenyl group-containing compound according to [2] above, wherein X in formula (1) is represented by formula (2-2).
[4]
A curable resin composition comprising the alkenyl group-containing compound according to any one of [1] to [3] above and a maleimide resin.
[5]
The curable resin composition according to [4] above, further comprising a radical polymerization initiator.
[6]
A cured product obtained by curing the curable resin composition according to [4] or [5] above.

The curable resin composition using the alkenyl group-containing compound of the present invention has excellent curability, and the cured product thereof has excellent electrical properties and heat resistance. In addition, the alkenyl group-containing compound of the present invention has high reactivity with maleimide groups, and there is almost no decrease in electrical properties due to phenolic hydroxyl groups. Therefore, insulating materials for electric and electronic parts (high reliability semiconductor encapsulation materials, etc.), laminates (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), liquid crystal encapsulants, organic EL encapsulants , adhesives (conductive adhesives, etc.), various composite materials including carbon fiber reinforced plastics (CFRP), paints, and the like.

1 is a ¹ H-NMR chart of the compound of Example 4 of the present invention. 1 is a ¹ H-NMR chart of the compound of Example 5 of the present invention. 1 is a ¹ H-NMR chart of the compound of Example 6 of the present invention. 1 is a ¹ H-NMR chart of the compound of Example 8 of the present invention. 1 is a ¹ H-NMR chart of the compound of Example 9 of the present invention.

The curable resin composition of the present invention is described in detail below.
The alkenyl group-containing compound used in the present invention is represented by the following formula (1).
In this specification, "-" represents a range including upper and lower limits (for example, 1 to 3 represents 1 or more and 3 or less).

In formula (1), Y represents an alkenyl group, and when multiple Ys are present, they may be the same or different. The alkenyl group of Y is not particularly limited, but from the viewpoint of curability and electrical properties, an alkenyl group having 1 to 5 carbon atoms is preferable, an alkenyl group having 1 to 3 carbon atoms is more preferable, and an allyl group and a methallyl group. , 1-propenyl group or 2-methylpropenyl group is more preferred, and allyl group or 1-propenyl group is particularly preferred.
Z represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms, and when multiple Z are present, they may be the same or different. From the viewpoint of electrical properties, Z is preferably a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
l represents a natural number from 1 to 6; Each of m and n is an integer of 0 or more, satisfies m+n=1 to 5, and at least one of 1 m is 1 or more.

In formula (1), X represents any organic group. X is not particularly limited as long as it is an organic group, but compounds having a biphenylene structure, a phenylene structure, an S-triazine structure, or a diphenylsulfone structure are preferred, and are represented by the following formulas (2-1) to (2-4). exemplified in the structure.

In formulas (2-1) to (2-4), * represents a bond to the oxygen atom of formula (1).
In formulas (2-1) to (2-4), l in the above formula (1) is 2 when the structure has two *, and l in the above formula (1) is 2 when the structure has three * 3.

More preferred structures for X in the formula (1) are structures represented by formulas (2-1) to (2-3), and formula (2-2) or formula (2-3) It is particularly preferred when it is the structure depicted.

The alkenyl group-containing compound of the present invention does not have a phenolic hydroxyl group as a reactive group. Therefore, the electrical properties are not deteriorated due to the phenolic hydroxyl group, and the radical polymerizability is excellent, so the polymer exhibits high heat resistance.

Next, the method for producing the alkenyl group-containing compound used in the present invention will be described.
The alkenyl group-containing compound used in the present invention can be produced using, for example, a compound having a phenolic hydroxyl group represented by the following formula (3) and an arbitrary halogen compound as raw materials.

In formula (3), Y, Z, m and n are the same as in formula (1).
Examples of compounds having a phenolic hydroxyl group represented by formula (3) include 2-allylphenol, 2-methallylphenol, 2-(2-propenyl)phenol, 2-(1-propenyl)phenol, eugenol, Examples include, but are not limited to, isoeugenol.

Any known halogen compound may be used as the arbitrary halogen compound. Preferred are those containing structures represented by the above formulas (2-1) to (2-4) in the molecule, such as o-xylylene difluoride, m-xylylene difluoride, p -xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m -xylylene diiodide, p-xylylene diiodide, 4,4'-bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisiodine methylenebiphenyl, 2,4'-bisfluoromethylenebiphenyl, 2,4'-bischloromethylenebiphenyl, 2,4'-bisbromomethylenebiphenyl, 2,4'-bisiodomethylenebiphenyl, 2,2'-bisfluoro methylenebiphenyl, 2,2'-bischloromethylenebiphenyl, 2,2'-bisbromomethylenebiphenyl, 2,2'-bisiodomethylenebiphenyl, and from the viewpoint of the reactivity of raw materials during synthesis, chloride compounds , bromide compounds and iodide compounds are preferred, and chloride compounds and bromide compounds are more preferred.

Optional halogen compounds other than the above include 2,2'-difluorodiphenylsulfone, 2,3'-difluorodiphenylsulfone, 2,4'-difluorodiphenylsulfone, 3,3'-difluorodiphenylsulfone, 3, 4'-difluorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 2,2'-dichlorodiphenylsulfone, 2,3'-dichlorodiphenylsulfone, 2,4'-dichlorodiphenylsulfone, 3,3'-dichlorodiphenyl Sulfone, 3,4'-dichlorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone, 2,2'-dibromodiphenylsulfone, 2,3'-dibromodiphenylsulfone, 2,4'-dibromodiphenylsulfone, 3,3 '-Dibromodiphenylsulfone, 3,4'-dibromodiphenylsulfone, 4,4'-dibromodiphenylsulfone, 2,2'-diiododiphenylsulfone, 2,3'-diiododiphenylsulfone, 2,4'-di iododiphenyl sulfone, 3,3'-diiododiphenyl sulfone, 3,4'-diiododiphenyl sulfone, 4,4'-diiododiphenyl sulfone, cyanuric fluoride, cyanuric chloride, cyanuric bromide, cyanuric iodide and the like. Fluoride-based compounds, chloride-based compounds, and bromide-based compounds are preferable, and more preferable are fluoride-based compounds and chloride-based compounds, from the viewpoint of the reactivity of raw materials during synthesis and the availability of raw materials. It is not limited.

The compound having a phenolic hydroxyl group represented by the formula (3) and the reaction with any halogen compound can be carried out by a known method. and a compound having a phenolic hydroxyl group to etherify.
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, N-methyl-2-pyrrolidone, etc. It is preferred to use The amount of the polar solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass, per 100 parts by mass of the total amount of raw materials (compound having a phenolic hydroxyl group and optional halogen compound). These highly polar solvents may be used alone or in combination, or may be used in combination with less polar solvents such as toluene and xylene. The amount of the low-polarity solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass, per 100 parts by mass of the total amount of raw materials (compound having a phenolic hydroxyl group and optional halogen compound).
More specifically, after dissolving the phenolic hydroxyl group-containing compound in dimethylformamide, dimethylsulfoxide, or the like, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, and the mixture is heated at 30 to 250°C to any desired temperature. A halogen compound is added over 1 to 10 hours and then reacted at 30 to 250° C. for 1 to 30 hours. After completion of the reaction, toluene, methyl isobutyl ketone, etc. are added, the by-product salts are removed by filtration, washing with water, etc., and the solvent such as toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure, and the reaction mixture is used in the present invention. can obtain an alkenyl group-containing compound.

The alkenyl group-containing compound used in the present invention may contain raw materials used in synthesis as impurities. If it does not contain any impurities, the solubility may decrease. On the other hand, when a large amount of impurities are contained, volatilization of the remaining raw materials occurs during the curing reaction, and there is concern about odors and adverse effects on the working environment. Impurities include, but are not limited to, raw materials and solvents used in synthesis. Examples thereof include compounds having a phenolic hydroxyl group represented by the above formula (3), and arbitrary halogen compounds used in the synthesis. The impurity content is preferably 0.0001 to 5%, more preferably 0.0001 to 3%, still more preferably 0.0001 to 1%.

The curable resin composition of the present invention may contain a maleimide resin.
A conventionally known maleimide resin can be used as the maleimide resin. Specific examples of maleimide resins include 4,4′-bismaleimidediphenylmethane, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2′-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3 '-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide , 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene and the like. From the viewpoint of solvent solubility, maleimide resins having a molecular weight distribution such as polyphenylmethane maleimide and maleimide resins described in JP-A-2009-001783 and JP-A-01-294662 are preferred. . These may be used alone or in combination of two or more. The amount of the maleimide resin compounded is preferably 0.5 to 5 times, more preferably 1 to 3 times, the mass ratio of the alkenyl group-containing compound represented by the formula (1).
Maleimide resins described in JP-A-2009-001783 and JP-A-01-294662 are particularly preferred because of their low hygroscopicity, flame retardancy and excellent dielectric properties.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator in order to allow the alkenyl groups of the alkenyl group-containing compound to react with each other or between the alkenyl group and the maleimide group. Radical polymerization initiators that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, 1,3-bis-(t-butylperoxy Isopropyl)-benzene and other dialkyl peroxides, t-butyl peroxybenzoate, 1,1-di-t-butylperoxycyclohexane and other peroxyketals, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butyl peroxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peresters such as benzoate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis(t-butylperoxydicarbonate) oxycarbonyloxy)hexane and other peroxycarbonates, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide and other organic peroxides and azobisisobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) known curing accelerators of azo compounds such as, but particularly limited to these not a thing Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator to be added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight may not be sufficiently elongated during the polymerization reaction.

The curable resin composition of the present invention may contain an epoxy resin. Any conventionally known epoxy resin can be used as the epoxy resin. Specific examples of epoxy resins include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensates of bisphenols and various aldehydes. and glycidyl ether-based epoxy resins obtained by glycidylating alcohols, alicyclic epoxies such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexane carboxylate. Resins, glycidylamine-based epoxy resins represented by tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester-based epoxy resins may be mentioned, but not limited to these. These may be used independently and may use 2 or more types.
In addition, epoxy resin obtained by dehydrochlorination reaction with epichlorohydrin using phenol aralkyl resin obtained by condensation reaction of phenol and bishalogenomethyl aralkyl derivative or aralkyl alcohol derivative as a raw material has low hygroscopicity and low hygroscopicity. It is particularly preferred as an epoxy resin because of its excellent flame resistance and dielectric properties.

When the curable resin composition of the present invention contains an epoxy resin, various epoxy resin curing agents and epoxy resin curing catalysts (curing accelerators) can be blended as necessary.
As epoxy resin curing agents, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, active ester resins and the like can be used. Specific examples of curing agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylols, biphenols and Modified products thereof, imidazoles, BF ₃ -amine complexes, guanidine derivatives and the like are included.
When using an active ester resin as a curing agent, 2 ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc. per molecule. A compound having at least The active ester curing agent is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound. agents are preferred.
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 equivalent of the epoxy group (or glycidyl group). If the amount is less than 0.5 equivalents or if the amount exceeds 1.5 equivalents with respect to 1 equivalent of epoxy groups, curing may be incomplete and good cured physical properties may not be obtained.

Examples of the epoxy resin curing catalyst (curing accelerator) include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl- imidazoles such as 2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl ) phenol, amines such as benzyldimethylamine, and phosphines such as triphenylphosphine, tributylphosphine and trioctylphosphine. The amount of the curing catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to the total 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may contain a cyanate ester resin. Conventionally known cyanate ester compounds can be used as the cyanate ester compound that can be blended in the curable resin composition of the present 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 polycondensates of bisphenols and various aldehydes. Examples include, but are not limited to, cyanate ester compounds obtained by reacting a condensate or the like 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, 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, and benzophenone.
Specific examples of cyanate ester compounds include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2′-bis(4-cyanatophenyl)propane, and bis(4-cyanatophenyl). methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2 , 2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, hydroxyl group of phenol/dicyclopentadiene cocondensate is converted to a cyanate group, but is not limited to these.
In addition, cyanate ester compounds whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferable as cyanate ester compounds because they are 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, and naphthenic acid are optionally used to trimerize the cyanate group to form a sym-triazine ring. Catalysts such as lead, zinc octoate, tin octoate, lead acetylacetonate, and dibutyltin maleate can also be incorporated into the curable resin composition of the present invention. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the total weight of the curable resin composition.

Furthermore, the curable resin composition of the present invention may optionally contain fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia. , powders such as aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers made of spherical or pulverized powders. can be done. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. is.

The curable resin composition of the present invention may optionally contain known additives. Specific examples of additives that can be used include polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, silicone gels, silicone oils, fillers such as silane coupling agents. Coloring agents such as surface treatment agents for materials, release agents, carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, relative to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention can be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. Addition of the solvent tends to lower the viscosity during preparation of the curable resin composition, improve the handling property, and further improve the impregnation property of the base material such as glass cloth. Solvents that can be used include, for example, γ-butyrolactones, amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone, and tetramethylenesulfone. Ether solvents such as sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone Aromatic solvents such as solvents, toluene and xylene can be mentioned. Moreover, when a laminate is produced, if the boiling point of the solvent used is too high, it may remain as a residual solvent. The boiling point of the solvent used is preferably 200° C. or lower, more preferably 180° C. or lower. The solvent is used in such a range that the solid concentration of the obtained varnish excluding the solvent is usually 10 to 80% by mass, preferably 20 to 70% by mass.

As the curing reaction of the curable resin composition of the present invention, all known reactions capable of reacting with unsaturated double bonds can be applied. Examples include radical polymerization, ene reaction, and Diels-Alder reaction. When curing using these reactions, unlike curing reactions that utilize ring-opening reactions of epoxy groups, polar groups are not generated during the curing process. less.
Moreover, the curable resin composition of the present invention can contain any alkenyl group-containing compound in the composition. Upon curing, radical polymerization can be utilized by combining the alkenyl compounds of the present invention with any alkenyl group-containing compound. Arbitrary alkenyl groups include substituted or unsubstituted linear, branched or cyclic alkenyl groups, which are not particularly limited as long as they are known, but preferred specific examples include vinyl, propenyl and butenyl. group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, cycloundecenyl group, cyclododecenyl group, cyclotridecenyl group, cyclotetradecenyl group, cyclo pentadecenyl group, cyclohexadecenyl group, cycloheptadecenyl group, cyclooctadecenyl group, cyclononadecenyl group, cycloeicosenyl group and the like, and polycyclic groups such as norbornyl group. Formula compounds are also included in this category. As the arbitrary alkenyl group, a C ₆ to C ₂₀ 1- to 4-ring alkenyl group is more preferable. Any number of hydrogen atoms in any alkenyl group may each be a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl groups, substituted or unsubstituted linear, branched or cyclic alkenyl groups, hydroxyl groups, alkoxy groups, amino groups, cyano groups, carbonyl groups, carboxyl groups and ester groups.

The method for preparing the curable resin composition of the present invention can be carried out according to known methods, but is not limited thereto. For example, each component may be mixed uniformly or may be prepolymerized. Specifically, the alkenyl group-containing compound represented by the formula (1) 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 epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenolic resin, an acid anhydride compound and other additives are added to the alkenyl group-containing compound represented by the formula (1) and the maleimide resin, if necessary. and may be prepolymerized. Mixing or prepolymerization of each component is performed by using, for example, an extruder, a kneader, rolls, etc. in the absence of a solvent, and using a reactor equipped with a stirrer in the presence of a solvent.

The curable resin composition of the present invention can be obtained, for example, by uniformly mixing the components described above in predetermined proportions. Further, for example, the curable resin composition of the present invention is usually precured at 130 to 180° C. for 30 to 500 seconds, and further post-cured at 150 to 200° C. for 2 to 15 hours. A sufficient curing reaction proceeds to obtain the cured product of the present invention. 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 composition.

The cured product of the curable resin composition of the present invention thus obtained has moisture resistance, heat resistance and high adhesiveness. Therefore, the curable 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 an insulating material, laminate (printed wiring board, BGA substrate, build-up substrate, etc.), sealing material, resist, and all other materials for electrical and electronic parts. In addition to molding materials and composite materials, it can also be used in fields such as paint materials and adhesives. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.
A semiconductor device has one encapsulated 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), TSOP (thin small outline package), and TQFP. (think quad flat package) and the like.

The curable resin composition of the present invention may be heated and melted to have a low viscosity and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. can. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, and poly paraphenylene terephthalamide (Kevlar®, manufactured by DuPont), wholly aromatic polyamides, polyesters; and organic fibers such as polyparaphenylene benzoxazole, polyimides and carbon fibers, but are particularly limited to these. not. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. Plain weave, Nanako weave, twill weave, and the like are known as weaving methods of woven fabric, and it is possible to appropriately select and use from these known methods depending on the intended use and performance. In addition, a woven fabric subjected to opening treatment or a glass woven fabric surface-treated with a silane coupling agent or the like is preferably used. Although the thickness of the base material is not particularly limited, it is preferably about 0.01 to 0.4 mm.
Furthermore, the prepreg is cut into a desired shape, and if necessary, after lamination with copper foil or the like, 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. By doing so, an electric/electronic laminate (printed wiring board) and a carbon fiber reinforcing material can be obtained.

EXAMPLES The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. In the examples, each physical property was measured under the following conditions.
<Melting point>
Measured by DSC. The value of the endothermic peak top was taken as the melting point.
Apparatus: Q-2000 TA-instruments Co., Ltd. Mode: M (modulated) DSC mode Heating rate: 10° C./min
Measurement temperature range: 30°C to 300°C
< ¹ H-NMR>
Device: JNM-ECS400 manufactured by JEOL Ltd.

(Example 1)
A flask equipped with a thermometer, condenser, and stirrer was charged with 15.0 parts by mass of cyanuric chloride, 40.8 parts by mass of toluene, 4.1 parts by mass of dimethylformamide, 32.9 parts by mass of 2-allylphenol, and 67 parts by mass of potassium carbonate. .6 parts by mass was added, and the internal temperature was raised to 100°C. The reaction is carried out at 100 ° C. for 6 hours, and after cooling, 200 parts by mass of toluene is added, washed with water, and concentrated under reduced pressure to obtain an etherification reaction product of cyanuric chloride and 2-allylphenol represented by the following formula (4) ( AP-CC) 37.9 parts by mass (yield 98%) was obtained. The melting point of the resulting reactant was 110°C.

(Example 2)
A flask equipped with a thermometer, condenser, and stirrer was charged with 18.4 parts by mass of cyanuric chloride, 50 parts by mass of toluene, 5.0 parts by mass of dimethylformamide, 40.3 parts by mass of 2-(1-propenyl)phenol, and carbonic acid. 82.9 parts by mass of potassium was added, and the internal temperature was raised to 100°C. The reaction is carried out at 100° C. for 6 hours, allowed to cool, 200 parts by mass of toluene is added, washed with water, and concentrated under reduced pressure to give an ether of cyanuric chloride represented by the following formula (5) and 2-(1-propenyl)phenol. 39.2 parts by mass (yield 82%) of a reaction product (PP-CC) was obtained. The melting point of the resulting reactant was 131°C.

(Example 3)
100 parts by mass of acetone, 18.4 parts by mass of cyanuric chloride, and 49.3 parts by mass of eugenol were added to a flask equipped with a thermometer, a condenser, and a stirrer, and stirring was started to raise the internal temperature to 30°C. 12.6 parts by mass of sodium hydroxide was added over 1.5 hours, and the reaction was carried out at 30°C for 6 hours. After removing acetone by concentration under reduced pressure, 100 g of toluene was added, washed with water, and concentrated under reduced pressure to obtain 47.6 of the etherification reaction product (Eu-CC) of cyanuric chloride and eugenol represented by the following formula (6). Part by mass (yield 84%) was obtained. The melting point of the resulting reactant was 125°C.

(Example 4)
40.3 parts by mass of 2-allylphenol, 117 parts by mass of dimethyl sulfoxide, and 58.8 parts by mass of water were added to a flask equipped with a thermometer, a condenser, and a stirrer, and stirring was started. 24.6 g of sodium hydroxide was added portionwise over 1 hour, and the internal temperature was raised to 70°C. 26.3 parts by mass of p-xylylene dichloride was added over 1 hour and reacted at 70° C. for 2 hours. After standing to cool, the precipitated crystals were separated by filtration, and 49.1 parts by mass of the etherification reaction product (AP-XLC) of p-xylene dichloride and 2-allylphenol represented by the following formula (7) (yield 88%). The melting point of the resulting reactant was 46°C. The measured ¹ H-NMR chart is shown in FIG.
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 4.98-5.08 (m, 4H), 5.13 (s, 4H), 5.97 (tt, 2H), 6.89 (t, 2H), 7.03 (d, 2H), 7.10-7.21 (m, 4H), 7.48 (s, 4H)

(Example 5)
40.3 parts by mass of 2-(1-propenyl)phenol, 117 parts by mass of dimethylsulfoxide, and 58.8 parts by mass of water were added to a flask equipped with a thermometer, a condenser, and a stirrer, and stirring was started. 24.6 g of sodium hydroxide was added portionwise over 1 hour, and the internal temperature was raised to 70°C. 26.3 parts by mass of p-xylylene dichloride was added over 1 hour and reacted at 70° C. for 2 hours. After standing to cool, the precipitated crystals were separated by filtration, and 49.0 mass of an etherification reaction product (PP-XLC) of p-xylene dichloride and 2-(1-propenyl)phenol represented by the following formula (8). part (88% yield). The melting point of the resulting reactant was 53°C. The measured ¹ H-NMR chart is shown in FIG.
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 1.72-1.89 (m, 6H), 5.10-5.18 (m, 6H), 5.70-7.52 ( m, 14H)

(Example 6)
A flask equipped with a thermometer, condenser, and stirrer was charged with 35.0 parts by mass of p-xylylene dichloride, 65.7 parts by mass of eugenol, 66.3 parts by mass of potassium carbonate, and 210 mL of dimethylformamide, and the mixture was stirred at room temperature for 6 hours. After the reaction, the temperature was raised to 70° C. and the reaction was carried out for 6 hours. 500 parts by mass of water was added to precipitate a solid, which was collected by filtration. The filtered solid was washed with a large amount of water, washed with a large amount of methanol, and dried at 80° C. for 12 hours to obtain an etherification reaction product of p-xylene dichloride and eugenol represented by the following formula (9) ( Eu-XLC) 78.6 parts by mass (yield 91%) was obtained. The melting point of the resulting reactant was 106°C. The measured ¹ H-NMR chart is shown in FIG.
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 3.29 (d, 4H), 3.73 (s, 6H), 4.99-5.12 (m, 8H), 5.94 (dq, 2H), 6.68 (d, 2H), 6.80 (s, 2H), 6.92 (d, 2H), 7.44 (s, 4H)

(Example 7)
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 35.0 parts by mass of p-xylylene dichloride, 65.7 parts by mass of isoeugenol, 66.3 parts by mass of potassium carbonate, and 210 mL of dimethylformamide. After reacting for 6 hours, the temperature was raised to 70° C. and the reaction was continued for 6 hours. 500 parts by mass of water was added to precipitate a solid, which was collected by filtration. The filtered solid was washed with a large amount of water and then with a large amount of methanol, and dried at 80° C. for 12 hours to obtain an etherification reaction product of p-xylene dichloride and isoeugenol represented by the following formula (10). (IEu-XLC) was obtained at 76.0 parts by mass (yield 88%). The melting point of the resulting reactant was 145.8°C.

(Example 8)
40.3 parts by mass of 2-allylphenol, 230 parts by mass of dimethyl sulfoxide, and 58.8 parts by mass of water were added to a flask equipped with a thermometer, condenser, and stirrer, and stirring was started. 24.6 g of sodium hydroxide was added portionwise over 1 hour, and the internal temperature was raised to 70°C. 37.7 parts by mass of p-bischloromethylenebiphenyl was added over 1 hour and reacted at 70° C. for 2 hours. The precipitated crystals were separated by filtration, and 60.9 parts by mass of an etherification reaction product (AP-BCMB) of p-bischloromethylenebiphenyl and 2-allylphenol represented by the following formula (11) (yield 91% )Met. The melting point of the resulting reactant was 105°C. The measured ¹ H-NMR chart is shown in FIG.
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 3.4 (d, 4H), 5.01-5.09 (m, 4H), 5.18 (s, 4H), 5.99 (tt, 2H), 6.91 (t, 2H), 7.05-7.25 (m, 6H), 7.65 (dd, 8H)

(Example 9)
20.2 parts by mass of 2-(1-propenyl)phenol, 230 parts by mass of dimethyl sulfoxide, and 29.4 parts by mass of water were added to a flask equipped with a thermometer, condenser, and stirrer, and stirring was started. 12.3 g of sodium hydroxide was added portionwise over 1 hour, and the internal temperature was raised to 70°C. 18.8 parts by mass of p-bischloromethylene biphenyl was added over 1 hour and reacted at 70° C. for 2 hours. The precipitated crystals are separated by filtration, and 31.3 parts by mass of an etherification reaction product (PP-BCMB) of p-bischloromethylenebiphenyl and 2-(1-propenyl)phenol represented by the following formula (12) ( Yield 93%) was obtained. The melting point of the resulting reactant was 164°C. The measured ¹ H-NMR chart is shown in FIG.
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 1.73-1.89 (m, 2H), 3.10-3.22 (m, 10H), 4.05-4.18 ( m, 4H), 5.12-5.22 (m, 2H), 5.72-7.78 (m, 12H)

(Example 10)
24.6 parts by mass of eugenol, 250 parts by mass of dimethylsulfoxide, and 29.4 parts by mass of water were added to a flask equipped with a thermometer, a condenser, and a stirrer, and stirring was started. 12.3 g of sodium hydroxide was added portionwise over 1 hour, and the internal temperature was raised to 70°C. 18.8 parts by mass of p-bischloromethylene biphenyl was added over 1 hour and reacted at 70° C. for 2 hours. The precipitated crystals were separated by filtration to obtain 31.9 parts by mass (yield 84%) of an etherification reaction product (Eu-BCMB) of p-bischloromethylenebiphenyl and eugenol represented by the following formula (13). rice field. The melting point of the resulting reactant was 102°C.

(Examples 11 to 19, Comparative Example 1)
The alkenyl group-containing compounds obtained in Examples 1, 2, 4, 5 and 9, the maleimide resin, and the radical polymerization initiator were blended in the proportions (parts by weight) shown in Table 1, heated, melted, and mixed in a metal container. It was poured into a mold and cured at 220° C. for 2 hours.
In Comparative Example 1, an epoxy resin, a maleimide resin, and the like were blended in the proportions (parts by weight) shown in Table 1, kneaded with a mixing roll, tableted, and a resin molded body was prepared by transfer molding. Cured at 220° C. for 6 hours.
Table 1 shows the results of measuring the physical properties of the cured product thus obtained with respect to the following items.

<Heat resistance test>
- Glass transition temperature: measured by a dynamic viscoelasticity tester, the temperature at which tan δ reaches its maximum value.
Measuring device: Q-800 manufactured by TA-instruments
Measurement temperature range: 30°C to 350°C
Heating rate: 2°C/min
Specimen size: 5mm x 50mm x 0.8mm
<Permittivity test/dielectric loss tangent test>
- Using a 1 GHz cavity resonator manufactured by Kanto Denshi Applied Development Co., Ltd., a test was performed by the cavity resonator perturbation method. However, the sample size was 1.7 mm wide×100 mm long and the thickness was 1.7 mm.

BMI: 4,4'-bismaleimidodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
MIR: Maleimide resin described in Example 4 of Japanese Patent Application Laid-Open No. 2009-001783 Epoxy resin: NC-3000-L (manufactured by Nippon Kayaku Co., Ltd.)
Phenolic resin: GPH-65 (manufactured by Nippon Kayaku Co., Ltd.)
2E-4MZ: 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
DCP: dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd.)

From the results in Table 1, it was confirmed that Examples 11 to 19 using the alkenyl group-containing compound of the present invention had excellent dielectric properties and high heat resistance.

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 changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on two Japanese patent applications (Japanese Patent Application No. 2018-74454, Japanese Patent Application No. 2018-74456) filed on April 9, 2018, which are incorporated by reference in their entirety. Also, all references cited herein are incorporated in their entirety.

Therefore, the alkenyl group-containing compound of the present invention can be used as an insulating material for electrical and electronic parts (such as a highly reliable semiconductor sealing material), a laminate (such as a printed wiring board, a BGA substrate, and a build-up substrate), an adhesive (a conductive adhesives, etc.), various composite materials such as CFRP, and coatings.

Claims (4)

An alkenyl group-containing compound represented by the following formula (1).

(In formula (1), X is a structure represented by the following formula (2-2) .Y represents an alkenyl group, and when there are multiple Ys, they may be the same or different. Z represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms, and when there are multiple Zs, they may be the same or different. Represents a natural number from 1 to 6. m and n are each an integer of 0 or more, satisfies m+n=1 to 5, and at least one of l m is 1 or more.)

(In formula (2-2), * represents a bond to the oxygen atom of formula (1).) A curable resin composition comprising the alkenyl group-containing compound according to claim 1 and a maleimide resin. 3. The curable resin composition according to claim 2 , further comprising a radical polymerization initiator. A cured product obtained by curing the curable resin composition according to claim 2 or 3 .

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