WO2019198607A1

WO2019198607A1 - Alkenyl-group-containing compound, curable resin composition, and cured object obtained therefrom

Info

Publication number: WO2019198607A1
Application number: PCT/JP2019/014920
Authority: WO
Inventors: 隆行遠島; 政隆中西; 篤彦長谷川; 一貴松浦
Original assignee: 日本化薬株式会社
Priority date: 2018-04-09
Filing date: 2019-04-04
Publication date: 2019-10-17
Also published as: JPWO2019198607A1

Abstract

An alkenyl-group-containing compound represented by formula (1), wherein X has a Hansen solubility parameter in which the polarity term δP is 6 or greater. (In formula (1), X represents any organic group; Y represents an alkenyl group, and when more than one Y is present, then the Y's may be the same or different; Z represents a hydrogen atom, a C_1-15 hydrocarbon group, or a C_1-15 alkoxy group, and when more than one Z is present, the Z's may be the same or different; l is a natural number of 1 to 6; and m and n are each an integer of 0 or larger and satisfy that m+n = 1 to 5, at least one of the l m's being 1 or larger.)

Description

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

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

In recent years, the required characteristics of laminated boards carrying electrical / electronic components have been broadened and advanced due to the expansion of their fields of use. Conventional semiconductor chips are mainly mounted on metal lead frames, but semiconductor chips with high processing capability such as a central processing unit (hereinafter referred to as CPU) are laminated plates made of a polymer material. More and more are being installed. As the processing speed of elements such as CPUs has increased and the clock frequency has increased, signal propagation delay and transmission loss have become a problem, so laminated boards are required to have low dielectric constants and low dielectric loss tangents. It has been. Further, as the processing speed of the device increases, the heat generation of the chip increases, so that improvement in heat resistance is also required at the same time.

In particular, as a semiconductor package (hereinafter referred to as PKG) used for smartphones is reduced in size, thickness, and density, there is a demand for a thin PKG substrate. Therefore, the heat generated when soldering the PKG to the mother board (PCB) causes problems such as a large warp. In order to reduce this, a PKG substrate material having a high Tg (for example, 260 ° C. or higher, and 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 communication equipment tends to increase year by year with the recent increase in capacity and speed, but the higher the signal frequency, the more electrical signals are converted into heat in the circuit. Therefore, transmission loss increases and it becomes difficult to transmit signals efficiently. In order to reduce this, a substrate material having a low dielectric loss tangent is also required.

In particular, in the 5G communication system “5G”, which is currently under development, 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 a low dielectric loss tangent material is increasing, and a dielectric loss tangent of 0.005 or less at 1 GHz is required. A material capable of achieving this heat resistance and dielectric characteristics (dielectric loss tangent) is required. Furthermore, in the automobile field, since digitization has progressed and precision electronic devices may be disposed near the engine drive unit, higher levels of heat resistance and moisture resistance are required. In addition, SiC semiconductors are beginning to be used in trains, air conditioners, and the like, and extremely high heat resistance is required for the sealing material of semiconductor elements, so that conventional epoxy resin sealing materials cannot be used.

However, since all of Patent Document 1 uses a phenol resin substituted with a propenyl group, the electrical characteristics are insufficient. In addition, in Patent Document 2, since all the phenolic resin substituted with an allyl group 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 a curing system is desired.

Japanese Laid-Open Patent Publication No. 04-359911 International Publication No. 2016/002704

The present invention has been made in view of such a situation, and is excellent in solvent solubility and has excellent heat resistance and electrical properties when cured, an alkenyl group-containing compound, and a curable resin composition containing the compound It aims at providing a thing and its hardened | cured material.

As a result of sincere and sincere studies to solve the above problems, the present inventors have found that a specific alkenyl group-containing compound is excellent in solvent solubility, and its cured product is excellent in heat resistance and electrical characteristics, and completes the present invention. It came to.
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, and when a plurality of Y are present, they may be the same or different. Z is a hydrogen atom or a carbon number. Represents a hydrocarbon group having 1 to 15 or an alkoxy group having 1 to 15 carbon atoms, and when there are a plurality of Z, they may be the same or different, and l represents a natural number of 1 to 6. m and n are each an integer of 0 or more, satisfying m + n = 1 to 5, and at least one of 1 m is 1 or more, and the polarity term δP value of the Hansen solubility parameter of X is 6 or more .)
[2]
The alkenyl group-containing compound according to [1], wherein the hydrogen bond term δH value of the Hansen solubility parameter of X in the formula (1) is 4 or more.
[3]
The alkenyl group according to [1] or [2] above, wherein X in the formula (1) contains any one of structures represented by the following formulas (2-1) to (2-3): Containing compound.

(In formulas (2-1) to (2-3), * represents a bond to an oxygen atom in formula (1).)
[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]
Furthermore, the curable resin composition of the preceding item [4] containing a radical polymerization initiator.
[6]
Hardened | cured material which hardened the curable resin composition of the preceding clause [4] or [5].

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

Hereinafter, the present invention will be described in detail.
The alkenyl group-containing compound of the present invention is represented by the following formula (1).
In the present specification, “to” 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 a plurality of Y are present, they may be the same or different. The alkenyl group for Y is not particularly limited, but is preferably an alkenyl group having 1 to 5 carbon atoms, more preferably an alkenyl group having 1 to 3 carbon atoms, and an allyl group or a methallyl group from the viewpoints of electrical properties and curability. 1-propenyl group or 2-methylpropenyl group is more preferable, and an allyl group or 1-propenyl group is particularly preferable.
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 a plurality of Z are present, they may be the same or different. 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, from the viewpoint of electrical characteristics. Or an alkoxy group having 1 to 6 carbon atoms.
l represents a natural number of 1 to 6. m and n are each an integer of 0 or more, satisfying m + n = 1 to 5, and at least one of 1 m is 1 or more. )

In formula (1), X represents an arbitrary organic group. X is not particularly limited as long as it is an organic group, but preferred structures include structures represented by the following formulas (2-1) to (2-3).

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

A more preferable structure as X in the formula (1) is a structure represented by the formula (2-1) or the formula (2-2), and a particularly preferable structure is represented by the formula (2-2). Structure.

The structure of the alkenyl group-containing compound of the present invention is designed using the Hansen solubility parameter. The Hansen solubility parameter is a predicted value of the solubility of the substance proposed by Hansen. The δD value indicates the London dispersion force, the δP value indicates the polar force, and δH indicates the hydrogen bonding force (Hansen, Charles. The three-dimensional solubility parameter). and solvent diffusion coefficient: see Tear importance in surface coating formation. Copenhagen: Danish Technical Press, 1967.).
In the formula (1), the polar term δP value of the Hansen solubility parameter of X is preferably 6 to 25, more preferably 8 to 22, and further preferably 10 to 20. When the δP value is in the above range, the compatibility with the polar solvent or the polar material is increased and the compatibility is improved.
When the δP value is 6 or more, compatibility with polar materials and polar solvents is improved. Further, when the δP value is 25 or less, the dielectric characteristics are good.
Since the alkenyl compound of the present invention has a high polarity and a molecular design that does not have a phenolic hydroxyl group as a reactive group, it has excellent heat resistance, solvent solubility, and dielectric properties.

In formula (1), the hydrogen bond term δH value of the Hansen solubility parameter of X is preferably 4 to 25, more preferably 6 to 22, and still more preferably 8 to 20. When the δH value is in the above range, the cured product has rigidity, so that the electrical characteristics do not deteriorate.

Next, the manufacturing method of the alkenyl group containing compound of this invention is demonstrated.
First, the alkenyl group-containing compound of the present invention can be produced using, for example, a compound having a phenolic hydroxyl group of the following formula (3) and an arbitrary halogen compound as a raw material.

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

Any known halogen compound may be used as long as it is a known one. Preferred are those containing in the molecule the structures represented by the above formulas (2-1) to (2-3), such as 2,2′-difluorodiphenylsulfone and 2,3′-difluorodiphenyl. Sulfone, 2,4'-difluorodiphenyl sulfone, 3,3'-difluorodiphenyl sulfone, 3,4'-difluorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 2,2'-dichlorodiphenyl sulfone, 2,3 '-Dichlorodiphenylsulfone, 2,4'-dichlorodiphenylsulfone, 3,3'-dichlorodiphenylsulfone, 3,4'-dichlorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone, 2,2'-dibromodiphenylsulfone 2,3′-dibromodiphenylsulfone, 2,4′-dibromodipheny Sulfone, 3,3′-dibromodiphenyl sulfone, 3,4′-dibromodiphenyl sulfone, 4,4′-dibromodiphenyl sulfone, 2,2′-diiododiphenyl sulfone, 2,3′-diiododiphenyl sulfone, 2 , 4'-diiododiphenylsulfone, 3,3'-diiododiphenylsulfone, 3,4'-diiododiphenylsulfone, 4,4'-diiododiphenylsulfone, cyanuric fluoride, cyanuric chloride, cyanuric bromide, cyanuric Iodide, 2,2'-difluorobenzophenone, 2,3'-difluorobenzophenone, 2,4'-difluorobenzophenone, 3,3'-difluorobenzophenone, 3,4'-difluorobenzophenone, 4,4'-difluorobenzophenone 2,2'-dichroic Benzophenone, 2,3′-dichlorobenzophenone, 2,4′-dichlorobenzophenone, 3,3′-dichlorobenzophenone, 3,4′-dichlorobenzophenone, 4,4′-dichlorobenzophenone, 2,2′-dibromobenzophenone, 2,3'-dibromobenzophenone, 2,4'-dibromobenzophenone, 3,3'-dibromobenzophenone, 3,4'-dibromobenzophenone, 4,4'-dibromobenzophenone, 2,2'-diiodobenzophenone, 2, 3,3′-diiodobenzophenone, 2,4′-diiodobenzophenone, 3,3′-diiodobenzophenone, 3,4′-diiodobenzophenone, 4,4′-diiodobenzophenone, etc. It is not limited to. From the viewpoint of the reactivity of the raw materials at the time of synthesis and the availability of the raw materials, preferred are fluoride compounds, chloride compounds, and bromide compounds, and more preferred are fluoride compounds and chloride compounds.

The reaction with the compound having a phenolic hydroxyl group represented by the formula (3) and any halogen compound can be carried out by a known method, and generally a halogen compound using a base such as an alkali metal hydroxide. And a compound having a phenolic hydroxyl group are reacted to be etherified.
At this time, a highly polar solvent such as methanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone is used. It is preferable to use it. The amount of the polar solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass with respect to 100 parts by mass of the total amount of the raw materials (the compound having a phenolic hydroxyl group and any halogen compound). These high-polarity solvents may be used alone or in combination, and low polarity solvents such as toluene and xylene may be used in combination. The amount of the low-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 total amount of raw materials (compound having a phenolic hydroxyl group and any halogen compound).
More specifically, after the phenolic hydroxyl group-containing compound is dissolved in the above dimethylformamide, dimethylsulfoxide, or the like, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, and any desired compound is added at 30 to 250 ° C. The 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, and the by-produced salt is removed by filtration, washing with water, etc., and further, the solvent such as toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure to thereby remove the alkenyl of the present invention. A group-containing compound can be obtained.

The alkenyl group-containing compound of the present invention can contain the raw materials used in the synthesis as impurities. If no impurities are contained, the solubility may be reduced. On the other hand, in the case where a large amount of impurities is contained, volatilization occurs in the remaining raw material during the curing reaction, and there is a concern about bad effects on odor and work commission environment. Examples of impurities include, but are not limited to, raw materials and solvents used for synthesis. For example, the compound which has the phenolic hydroxyl group represented by the said Formula (3), the arbitrary halogen compounds used for the synthesis | combination, etc. are mentioned. The impurity content is preferably 0.0001 to 5%, more preferably 0.0001 to 3%, and 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 the maleimide resin include 4,4′-bismaleimide diphenylmethane, polyphenylmethane maleimide, m-phenylenebismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3 '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, and the like. From the viewpoint of solvent solubility, polyphenylmethane maleimide and maleimide resins having a molecular weight distribution such as maleimide resins described in Japanese Patent Application Laid-Open No. 2009-001783 and Japanese Patent Application Laid-Open No. 01-294661 are preferable. These may be used alone or in combination of two or more. The compounding amount of the maleimide resin is preferably in the range of 0.5 to 5 times, more preferably 1 to 3 times by mass ratio with respect to the alkenyl group-containing compound represented by the formula (1).
In addition, maleimide resins described in Japanese Patent Application Laid-Open No. 2009-001783 and Japanese Patent Application Laid-Open No. 01-294661 are particularly preferable because they are excellent in low moisture absorption, flame retardancy, and dielectric properties.

In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator to react alkenyl groups of the alkenyl group-containing compound with each other or between the alkenyl group and the maleimide group. Examples of the radical polymerization initiator that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis- (t-butylperoxy). Dialkyl peroxides such as isopropyl) -benzene, peroxyketals such as t-butylperoxybenzoate, 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butyl peroxy-2-ethylhexanoe , Alkyl peresters such as t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxybenzoate, di Peroxy such as -2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane Organic peroxides such as carbonates, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, lauroyl peroxide, azobisisobutyronitrile, 4,4′-azobis (4-cyano Valeric acid), 2,2′-azobis (2,4- Known curing accelerators for azo compounds such as (dimethylvaleronitrile) can be mentioned, but are not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, and the like are preferable, and dialkyl peroxides are more preferable. The addition amount of the radical polymerization initiator is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight may not be sufficiently extended during the polymerization reaction.

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

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 the epoxy resin curing agent, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, active ester resins, and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substituted) Polymerization of phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols and various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, imidazo - Le, BF 3 _- amine complex, guanidine derivatives.
When an active ester resin is used as a curing agent, two ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters in one molecule. Compounds having the above are preferred. The active ester curing agent is preferably obtained by a condensation reaction between 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 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 1 equivalent of epoxy group (or glycidyl group). When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete, and good cured 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) ) Amines such as phenol and benzyldimethylamine, and phosphines such as triphenylphosphine, tributylphosphine and trioctylphosphine. The compounding amount of the curing catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the curable resin composition.

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

In the case where the curable resin composition of the present invention contains a cyanate resin, zinc naphthenate, cobalt naphthenate, copper naphthenate, naphthenic acid are used to form a sym-triazine ring by trimerizing cyanate groups as necessary. Catalysts such as lead, zinc octylate, tin octylate, lead acetylacetonate, and dibutyltin maleate can also be included in the curable resin composition of the present invention. The catalyst is generally used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, based on 100 parts by weight of the total weight of the curable resin composition.

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

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

The curable resin composition of the present invention can be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. By adding a solvent, the viscosity at the time of preparation of the curable resin composition is lowered, the handling property is improved, and the impregnation property to a substrate such as a glass cloth tends to be further improved. Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned. Moreover, when producing a laminated board, when the boiling point of the solvent to be used is too high, it may remain as a residual solvent. As a boiling point of the solvent to be used, 200 degrees C or less is preferable, More preferably, it is 180 degrees C or less. The solvent is used in the range where the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by mass, preferably 20 to 70% by mass.

As the curing reaction of the curable resin composition of the present invention, all known reactions that can react with unsaturated double bonds can be applied. For example, radical polymerization, ene reaction, Diels-Alder reaction and the like can be mentioned. When curing using these reactions, unlike the curing reaction that utilizes the ring-opening reaction of epoxy groups, polar groups are not generated during the curing process, resulting in poor water absorption and electrical properties due to improved heat resistance. Is less.
The curable resin composition of the present invention can contain any alkenyl group-containing compound in the composition. At the time of curing, radical polymerization by a combination of the alkenyl compound described in the present invention and an arbitrary alkenyl group-containing compound can be utilized. The arbitrary alkenyl group includes a substituted or unsubstituted linear, branched or cyclic alkenyl group, and is not particularly limited as long as it is a known alkenyl group. Preferred specific examples include vinyl group, propenyl group, 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, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclo Tetradecenyl group, cyclopentadecenyl group, cyclohexadecenyl group, cycloheptadecenyl group, cyclooctadecenyl group, cyclononadecenyl group, cycloeicocenyl group, etc., and norbornyl group Such polycyclic compounds are also included in this category. Further, as the arbitrary alkenyl group, a C ₆ -C ₂₀ 1-4 alkenyl group is more preferable. In addition, any number of hydrogen atoms in any alkenyl group is a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl, respectively. It may be substituted with a group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, hydroxyl group, alkoxy group, amino group, cyano group, carbonyl group, carboxyl group or ester group.

The preparation method of the curable resin composition of the present invention can be carried out according to a known method, but is not limited thereto. For example, each component may be simply mixed or 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 phenol 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 as necessary. Then, it may be prepolymerized. For mixing or prepolymerization of each component, for example, an extruder, a kneader, or a roll is used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.

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

The cured product of the curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, and high adhesion. 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 a material for all electrical and electronic components such as an insulating material, a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, and a resist. In addition to molding materials and composite materials, they can also be used in fields such as paint materials and adhesives. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.
A semiconductor device has what was sealed with the curable resin composition of this invention. As semiconductor devices, for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).

The curable resin composition of the present invention can also be obtained by melting by heating, lowering the viscosity, and impregnating it with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. . 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, and inorganic fibers other than glass and poly glass. Paraphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fiber, but are particularly limited to these. Not. Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat etc. are mentioned. Moreover, as a weaving method of the woven fabric, a plain weave, a nanako weave, a twill weave and the like are known, and these can be appropriately selected and used according to the intended use and performance. Further, a woven fabric that has been subjected to fiber opening treatment or a glass woven fabric that has been surface treated with a silane coupling agent or the like is preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm.
Furthermore, the above prepreg is cut into a desired shape, laminated with copper foil if necessary, and the curable resin composition is heated and cured while applying pressure to the laminate by a press molding method, autoclave molding method, sheet winding molding method, etc. By doing so, it is possible to obtain an electric / electronic laminate (printed wiring board) 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, Hansen Solubility Parameters were measured using Hansen Solubility Parameter in Practice (HSPIP) Ver. Calculated using 5.0 (Charles M. Hansen).
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, Inc. Mode: M (modulate) DSC mode Temperature rising rate: 10 ° C./min
Measurement temperature range: 30 ° C to 300 ° C
^<1 H-NMR>
Device: JNM-ECS400 JEOL Ltd.

Example 1
To a flask equipped with a thermometer, a condenser, and a stirrer, 80.5 parts by mass of 2-allylphenol, 65.5 parts by mass of difluorobenzophenone, 300 parts by mass of dimethyl sulfoxide, and 166 parts by mass of potassium carbonate were added. Reacted for hours. By adding 500 parts by mass of toluene, washing with water, and concentrating under reduced pressure, 130 parts by mass of etherification reaction product (AP-BP) of semisolid resinous difluorobenzophenone and 2-allylphenol represented by the following formula (4) Part (yield 97%).
In the formula (4), the Hansen solubility parameter of the structure corresponding to X in the formula (1) has a δP value of 6.7 and a δH value of 4.3.

(Example 2)
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 26.8 parts by mass of 2- (1-propenyl) phenol, 21.8 parts by mass of difluorobenzophenone, 100 parts by mass of dimethyl sulfoxide, and 55.2 parts by mass of potassium carbonate. In addition, the mixture was reacted at 100 ° C. for 20 hours. By adding 200 parts by mass of toluene, washing with water, and concentrating under reduced pressure, etherification reaction product (PP-BP) 32.4 of difluorobenzophenone and 2- (1-propenyl) phenol represented by the following formula (5): Part by mass (yield 73%) was obtained. The melting point of the obtained reaction product was 110 ° C.
In the formula (5), the Hansen solubility parameter of the structure corresponding to X in the formula (1) has a δP value of 6.7 and a δH value of 4.3.

(Example 3)
To a flask equipped with a thermometer, condenser, and stirrer, 32.8 parts by weight of eugenol, 21.8 parts by weight of difluorobenzophenone, 100 parts by weight of dimethyl sulfoxide, and 55.2 parts by weight of potassium carbonate were added, and the mixture was heated at 100 ° C for 20 hours. Reacted. After adding 200 parts by mass of toluene, washing with water, and concentrating under reduced pressure, 47.4 parts by mass of etherification reaction product (Eu-BP) of semisolid resinous difluorobenzophenone and eugenol represented by the following formula (6) (93% yield) was obtained.
In the formula (6), the Hansen solubility parameter of the structure corresponding to X in the formula (1) has a δP value of 6.7 and a δH value of 4.3.

Example 4
In a flask equipped with a thermometer, condenser, and stirrer, 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, 67 of potassium carbonate .6 parts by mass was added, and the internal temperature was raised to 100 ° C. The reaction was carried out at 100 ° C. for 6 hours. After standing to cool, 200 parts by mass of toluene was added, washed with water, and concentrated under reduced pressure to give an etherification reaction product of cyanuric chloride and 2-allylphenol represented by the following formula (7) ( AP-CC) 37.9 parts by mass (yield 98%) was obtained. The melting point of the obtained reaction product was 110 ° C.
In the formula (7), the Hansen solubility parameter of the structure corresponding to X in the formula (1) has a δP value of 19.6 and a δH value of 15.2).

(Example 5)
In a flask equipped with a thermometer, condenser, and stirrer, 18.4 parts by weight of cyanuric chloride, 50 parts by weight of toluene, 5.0 parts by weight of dimethylformamide, 40.3 parts by weight of 2- (1-propenyl) phenol, carbonic acid 82.9 parts by mass of potassium was added, and the internal temperature was raised to 100 ° C. The reaction was carried out at 100 ° C. for 6 hours. After standing to cool, 200 parts by mass of toluene was added, washed with water, and concentrated under reduced pressure to give ether of cyanuric chloride and 2- (1-propenyl) phenol represented by the following formula (8). Reaction product (PP-CC) 39.2 parts by mass (yield 82%) was obtained. The melting point of the obtained reaction product was 131 ° C.
In the formula (8), the δP value of the Hansen solubility parameter of the structure corresponding to X in the formula (1) is 19.6, and the δH value is 15.2.

(Example 6)
To a flask equipped with a thermometer, a condenser, and a stirrer, 100 parts by mass of acetone, 18.4 parts by mass of cyanuric chloride and 49.3 parts by mass of eugenol were added and stirring was started, and the internal temperature was raised to 30 ° C. 12.6 parts by mass of sodium hydroxide was added over 1.5 hours and reacted at 30 ° C. for 6 hours. Acetone was removed by concentration under reduced pressure, 100 g of toluene was added, washed with water, and concentrated under reduced pressure to obtain 47.6 etherified reaction product (Eu-CC) of cyanuric chloride and eugenol represented by the following formula (9). Part by mass (yield 84%) was obtained. The melting point of the obtained reaction product was 125 ° C.
In the formula (9), the Hansen solubility parameter of the structure corresponding to X in the formula (1) has a δP value of 19.6 and a δH value of 15.2.

(Synthesis Example 1)
To a flask equipped with a thermometer, a condenser, and a stirrer, 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, and stirring was started. Sodium hydroxide (12.3 g) was added in portions over 1 hour, and the internal temperature was raised to 70 ° C. 18.8 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 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 (10) ( Yield 93%) was obtained. The melting point of the obtained reaction product was 164 ° C.
In the formula (10), the δP value of the Hansen solubility parameter of the structure corresponding to X in the formula (1) is 1.4, and the δH value is 10.2.

(Examples 8 to 14, Comparative Examples 1 and 2)
The alkenyl group-containing compound, maleimide resin, and radical polymerization initiator obtained in Examples 2, 4, and 5 and Synthesis Example 1 were blended in the proportions (parts by weight) shown in Table 1, and heated, melted and mixed in a metal container. It was poured into a mold as it was and cured at 220 ° C. for 2 hours.
The results of measuring the physical properties of the cured product thus obtained for the following items are shown in Table 1.
In Comparative Example 2, various epoxy resins, maleimide resins, and curing catalysts were blended in the proportions (parts by weight) shown in Table 1, kneaded with a mixing roll, tableted, and then a resin molded body was prepared by transfer molding, at 200 ° C. It was cured for 2 hours and further at 220 ° C. for 6 hours. The results of measuring the physical properties of the cured product thus obtained for the following items are shown in Table 1.

<Heat resistance test>
Glass transition temperature: Temperature measured by a dynamic viscoelasticity tester and tan δ is a maximum value.
Measuring device: Q-800, manufactured by TA-instruments
Measurement temperature range: 30 ° C-350 ° C
Temperature increase rate: 2 ° C / min
(Specimen size: 5mm x 50mm x 0.8mm)
<Dielectric constant test and dielectric loss tangent test>
-Using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd., a test was performed by the cavity resonator perturbation method. However, the test was conducted with a sample size of 1.7 mm wide × 100 mm long and a thickness of 1.7 mm.
<Solvent solubility>
-10.0 g of alkenyl group-containing compound (not mixed with maleimide resin) and 10.0 g of methyl ethyl ketone were weighed into a 100 ml flask equipped with a condenser, heated to 70 ° C and stirred for 30 minutes. After 30 minutes, visual judgment was made, and when the alkenyl group-containing compound was dissolved, it was marked with ◯, and when the alkenyl group-containing compound was not completely dissolved, x was marked.

BMI: 4,4′-bismaleimide diphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
MIR: Maleimide resin epoxy resin described in Example 4 of Japanese Unexamined Patent Publication No. 2009-001783: NC-3000-L (manufactured by Nippon Kayaku Co., Ltd.)
Phenolic resin: GPH-65 (Nippon Kayaku Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
DCP: Dicumyl peroxide (manufactured by Kayaku Akzo)
δP value: the numerical value of the polar term of the Hansen solubility parameter of X in the formula (1) δH value: the numerical value of the hydrogen bond term of the Hansen solubility parameter of X in the formula (1)

From the results shown in Table 1, it was confirmed that Examples 4 to 8 using the alkenyl group-containing compound of the present invention had excellent dielectric properties, high heat resistance, and excellent solvent solubility.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on two Japanese patent applications (Japanese Patent Application Nos. 2018-74555 and 2018-74456) filed on April 9, 2018, which are incorporated by reference in their entirety. Also, all references cited herein are incorporated as a whole.

Therefore, the alkenyl group-containing compound of the present invention comprises an insulating material for electrical and electronic parts (such as a highly reliable semiconductor encapsulating material), a laminate (such as a printed wiring board, a BGA substrate, a build-up substrate), an adhesive (conductive). It is useful for applications such as adhesives, various composite materials including CFRP, and paints.

Claims

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, and when a plurality of Y are present, they may be the same or different. Z is a hydrogen atom or a carbon number. Represents a hydrocarbon group having 1 to 15 or an alkoxy group having 1 to 15 carbon atoms, and when there are a plurality of Z, they may be the same or different, and l represents a natural number of 1 to 6. m and n are each an integer of 0 or more, satisfying m + n = 1 to 5, and at least one of 1 m is 1 or more, and the polarity term δP value of the Hansen solubility parameter of X is 6 or more .)
The alkenyl group-containing compound according to claim 1, wherein the hydrogen bond term δH value of the Hansen solubility parameter of X in the formula (1) is 4 or more.
The alkenyl group-containing compound according to claim 1 or 2, wherein X in the formula (1) contains any one of structures represented by the following formulas (2-1) to (2-3).

(In formulas (2-1) to (2-3), * represents a bond to an oxygen atom in formula (1).)
A curable resin composition comprising the alkenyl group-containing compound according to any one of claims 1 to 3 and a maleimide resin.
Furthermore, the curable resin composition of Claim 4 containing a radical polymerization initiator.
A cured product obtained by curing the curable resin composition according to claim 4 or 5.