CN111918889B - Alkenyl group-containing compound, curable resin composition, and cured product thereof - Google Patents
Alkenyl group-containing compound, curable resin composition, and cured product thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/04—Homopolymers or copolymers of nitriles
Abstract
An alkenyl-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, the plurality of Y 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 a plurality of Z are present, the plurality of Z may be the same or different. 1 represents a natural number of 1 to 6. m and n are each an integer of 0 or more, m + n =1 to 5 is satisfied, and at least one of the 1m present is 1 or more. )
Description
Technical Field
The present invention relates to an alkenyl group-containing compound, a curable resin composition, and a cured product thereof, which are suitably used for a sealing material for a semiconductor element, a sealing material for a liquid crystal display element, a sealing material for an organic Electroluminescence (EL) element, an electric and electronic component such as a printed wiring board and a build-up laminate, and a composite material for a lightweight high-strength structural material such as a carbon fiber-reinforced plastic and a glass fiber-reinforced plastic.
Background
In recent years, a laminate board on which electric and electronic parts are mounted has been required to have a wide range of characteristics and improved properties due to the expansion of its application field. While conventional semiconductor chips are mainly mounted on metal lead frames, semiconductor chips having high processing capability such as a central processing unit (hereinafter, referred to as CPU) are often mounted on a laminate made of a polymer material. As the processing speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become problems, and thus, reduction of dielectric constant and reduction of dielectric loss tangent are required for laminated boards. Further, as the processing speed of the device increases, heat generation of the chip increases, and therefore, improvement of heat resistance is also required.
In particular, with the miniaturization, thinning, and densification of semiconductor packages (hereinafter referred to as PKGs) used in smartphones and the like, thinning of PKG substrates is required, but when the PKG substrates become thinner, the rigidity decreases, and therefore, there is a problem that large warpage occurs due to heating when the PKGs are solder-mounted on a motherboard (PCB). In order to reduce such a problem, a PKG substrate material having a high Tg (for example, 260 ℃ or higher and, in recent years, 288 ℃ or higher) at a solder mounting temperature or higher is required.
On the other hand, with the recent increase in capacity and high-speed communication, the frequency of electric signals handled by information communication equipment tends to increase year by year, but the higher the signal frequency, the more the electric signals are converted into heat in the circuit, so the transmission loss increases, and it is difficult to efficiently transmit the signals. In order to reduce this, a substrate material having a low dielectric loss tangent is also required.
Particularly, in the 5 th generation communication system "5G" which is currently under accelerated development, it is expected that data communication of various devices such as a smartphone will be further advanced to increase capacity and high-speed communication. The demand for low dielectric loss tangent materials is increasing, and dielectric loss tangent of 0.005 or less at least at 1GHz is required, and materials capable of realizing the heat resistance and dielectric characteristics (dielectric loss tangent) are required. Further, in the automotive field, electronic devices are being developed, and there are cases where precision electronic devices are disposed in the vicinity of an engine drive unit, and therefore higher levels of heat resistance and moisture resistance are required. Further, siC semiconductors have come to be used in electric cars, air conditioners, and the like, and extremely high heat resistance is required for sealing materials for semiconductor elements, and therefore conventional epoxy resin sealing materials cannot meet the requirements.
However, in patent document 1, a phenol resin in which all acryl groups are substituted is used, and thus the electrical characteristics are insufficient. In addition, in patent document 2, since a phenol resin in which all of the phenol resins are 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, and development of a material and a curing system capable of achieving both high heat resistance and electrical characteristics is desired.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H04-359911
Patent document 2: international publication No. 2016/002704
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an alkenyl group-containing compound which exhibits excellent heat resistance and electrical characteristics when cured, a curable resin composition, and a cured product thereof.
Means for solving the problems
The present inventors have diligently studied to solve the above problems and as a result, have found that the use of a specific alkenyl group-containing compound provides a cured product excellent in heat resistance and electrical characteristics, and have completed the present invention.
That is, the present invention relates to the following [1] to [6].
[1]
An alkenyl-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, the plurality of Y may be the same or different. Z independently 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, the plurality of Z may be the same or different. 1 represents a natural number of 1 to 6. m and n are each an integer of 0 or more, m + n =1 to 5 is satisfied, and at least one of the 1m present is 1 or more. )
[2]
The alkenyl-containing compound according to the above item [1], wherein X in the formula (1) contains any one of the structures represented by the following formulae (2-1) to (2-4).
(in formulae (2-1) to (2-4),. The symbol represents bonding to the oxygen atom in formula (1).)
[3]
The alkenyl group-containing compound according to the aforementioned item [2], wherein X in the formula (1) is represented by the formula (2-2).
[4]
A curable resin composition comprising a maleimide resin and the alkenyl group-containing compound according to any one of the preceding items [1] to [3 ].
[5]
The curable resin composition according to item [4], wherein the curable resin composition further comprises a radical polymerization initiator.
[6]
A cured product obtained by curing the curable resin composition according to the above item [4] or [5 ].
Effects of the invention
The curable resin composition using the alkenyl group-containing compound of the present invention has excellent curability, and a cured product thereof has excellent electrical characteristics and heat resistance. In addition, the alkenyl-containing compound of the present invention has high reactivity with maleimide groups, and hardly causes deterioration of electrical characteristics due to phenolic hydroxyl groups. Therefore, the resin composition can be used for various composite materials and paints represented by insulating materials (high-reliability semiconductor sealing materials and the like) for electric and electronic parts, laminated boards (printed circuit boards, ball Grid Array (BGA) substrates, laminated substrates and the like), liquid crystal sealing materials, organic EL sealing materials, adhesives (conductive adhesives and the like), carbon Fiber Reinforced Plastics (CFRP) and the like.
Drawings
FIG. 1 is a drawing of a compound of example 4 of the present invention 1 H-NMR chart.
FIG. 2 is a drawing of the compound of example 5 of the present invention 1 H-NMR chart.
FIG. 3 is a drawing of a compound of example 6 of the present invention 1 H-NMR chart.
FIG. 4 is a photograph of a compound of example 8 of the present invention 1 H-NMR chart.
FIG. 5 is a photograph of a compound of example 9 of the present invention 1 H-NMR chart.
Detailed Description
The curable resin composition of the present invention will be described in detail below.
The alkenyl-containing compound used in the present invention is represented by the following formula (1).
In the present specification, "to" represents a range including an upper limit and a lower limit (for example, 1 to 3, inclusive, represents 1 to 3 inclusive).
In formula (1), Y represents an alkenyl group, and when there are a plurality of Y, the plurality of Y may be the same or different. The alkenyl group Y is not particularly limited, but from the viewpoint of curability and electrical characteristics, an alkenyl group having 1 to 5 carbon atoms is preferable, an alkenyl group having 1 to 3 carbon atoms is more preferable, an allyl group, a methallyl group, a 1-propenyl group, or a 2-methylpropenyl group is further preferable, and an allyl group or a 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, the plurality of Z may be the same or different. From the viewpoint of electrical characteristics, 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, and more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
1 represents a natural number of 1 to 6. m and n are each an integer of 0 or more, m + n =1 to 5 is satisfied, and at least one of the 1m present 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, and is preferably a compound having a biphenylene structure, a phenylene structure, an s-triazine structure, or a diphenylsulfone structure, and exemplified by the structures represented by the following formulae (2-1) to (2-4).
In formulae (2-1) to (2-4), represents bonding to the oxygen atom in formula (1).
In formulas (2-1) to (2-4), 1 in formula (1) is 2 when having 2 × and 1 in formula (1) is 3 when having 3 × structure.
More preferred structures for X in the formula (1) are those represented by the formulae (2-1) to (2-3), and particularly preferred are those represented by the formulae (2-2) or (2-3).
The alkenyl-containing compound of the present invention does not have a phenolic hydroxyl group as a reactive group. Therefore, the composition shows high heat resistance because the composition has no deterioration in electrical characteristics due to phenolic hydroxyl groups and is excellent in radical polymerizability.
Next, a 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, for example, from 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).
As the compound having a phenolic hydroxyl group represented by the formula (3), for example, there can be mentioned: 2-allylphenol, 2-methallylphenol, 2- (2-propenyl) phenol, 2- (1-propenyl) phenol, eugenol, isoeugenol, and the like, but are not limited thereto.
Any halogen compound may be used as long as it is a known halogen compound. Preferred examples thereof include halogen compounds having a structure represented by the above formulae (2-1) to (2-4) in the molecule, and examples thereof include: <xnotran> 1,2- ( ) ,1,3- ( ) ,1,4- ( ) ,1,2- () ,1,3- () ,1,4- () ,1,2- ( ) ,1,3- ( ) ,1,4- ( ) ,1,2- ( ) ,1,3- ( ) ,1,4- ( ) ,4,4 '- ( ) ,4,4' - () ,4,4 '- ( ) ,4,4' - ( ) ,2,4 '- ( ) ,2,4' - () ,2,4 '- ( ) ,2,4' - ( ) ,2,2 '- ( ) ,2,2' - () ,2,2 '- ( ) ,2,2' - ( ) , , , , , , </xnotran> A bromide compound.
In addition, as arbitrary halogen compounds other than the above, there can be mentioned: 2,2 '-difluorodiphenyl sulfone, 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' -dichlorodiphenyl sulfone, 2,4 '-dichlorodiphenyl sulfone, 3,3' -dichlorodiphenyl sulfone, 3,4 '-dichlorodiphenyl sulfone, 4,4' -dichlorodiphenyl sulfone, 2,2 '-dibromodiphenyl sulfone, 2,3' -dibromodiphenyl sulfone, 2,4 '-dibromodiphenyl sulfone, 3,3' -dibromodiphenyl sulfone, 3,4 '-dibromodiphenyl sulfone, 4,4' -dibromodiphenyl sulfone, 2,2 '-diiododiphenyl sulfone, 2,3' -diiododiphenyl sulfone, 2,4 '-diiododiphenyl sulfone, 3,3' -diiododiphenyl sulfone, 3,4 '-diiododiphenyl sulfone, 4' -diiododiphenyl sulfone, cyanuric fluoride, cyanuric chloride, cyanuric bromide, cyanuric chloride, etc., from the viewpoint of reactivity of raw materials at the time of synthesis and easy availability of raw materials, fluoride-based compounds, chloride-based compounds, and bromide-based compounds are preferable, and fluoride-based compounds and chloride-based compounds are more preferable, but not limited thereto.
The reaction of the compound having a phenolic hydroxyl group represented by the above formula (3) with an arbitrary halogen compound can be carried out by a known method, and the etherification is usually carried out by reacting the halogen compound with the compound having a phenolic hydroxyl group using a base such as an alkali metal hydroxide.
In this case, it is preferable to use 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, or N-methyl-2-pyrrolidone. The amount of the polar solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass, based on 100 parts by mass of the total amount of the raw materials (the compound having a phenolic hydroxyl group and the optional halogen compound). These highly polar solvents may be used alone or in combination, or a solvent having a low polarity such as toluene or xylene may be used in combination. The amount of the low-polarity solvent used is usually 50 to 400 parts by mass, preferably 70 to 300 parts by mass, relative to 100 parts by mass of the total amount of the raw materials (the compound having a phenolic hydroxyl group and the optional halogen compound).
More specifically, a compound having a phenolic hydroxyl group is dissolved in the aforementioned dimethylformamide, dimethylsulfoxide, etc., then an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, and an arbitrary halogen compound is added at 30 to 250 ℃ for 1 to 10 hours, followed by reaction at 30 to 250 ℃ for 1 to 30 hours. After the completion of the reaction, toluene, methyl isobutyl ketone, or the like is added, and a salt formed as a by-product is removed by filtration, washing with water, or the like, and the solvent such as toluene, methyl isobutyl ketone, or the like is further distilled off under heating and reduced pressure, whereby the alkenyl-containing compound used in the present invention can be obtained.
The alkenyl-containing compound used in the present invention may contain a raw material used in synthesis as an impurity. If the impurities are not contained at all, the solubility may be lowered. On the other hand, when a large amount of impurities are contained, the residual raw materials are volatilized during the curing reaction, and there is a fear that odor is generated and the working environment is adversely affected. Examples of the impurities include, but are not limited to, raw materials and solvents used in synthesis. For example, a compound having a phenolic hydroxyl group represented by the above formula (3), an arbitrary halogen compound used in synthesis, and the like can be mentioned. The content of the impurity 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.
As the maleimide resin, a conventionally known maleimide resin can be used. Specific examples of the maleimide resin include 4,4' -bismaleimidodiphenylmethane, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylenebismaleimide, 4' -diphenyletherbismaleimide, 4' -diphenylsulfonebismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, and 1, 3-bis (4-maleimidophenoxy) benzene. From the viewpoint of solvent solubility, maleimide resins having a molecular weight distribution, such as polyphenylmethane maleimide, the maleimide resins described in Japanese patent laid-open Nos. 2009-001783 and 01-294662, are preferred. These maleimide resins may be used alone or in combination of two or more. The amount of the maleimide resin blended is preferably in the range of 0.5 to 5 times, more preferably in the range of 1 to 3 times in terms of mass ratio, relative to the alkenyl group-containing compound represented by the above formula (1).
The maleimide resins described in jp 2009-001783 a and jp 01-294662 a are particularly preferred because of their low hygroscopicity, flame retardancy, and excellent dielectric properties.
In the curable resin composition of the present invention, a radical polymerization initiator is preferably used in order to react alkenyl groups of the alkenyl group-containing compound with each other and to react the alkenyl group with 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; dialkyl peroxides such as dicumyl peroxide and 1, 3-bis (t-butylperoxyisopropyl) benzene; peroxyketals such as t-butyl peroxybenzoate and 1, 1-di-t-butyl peroxycyclohexane; alkyl peresters such as α -cumyl peroxyneodecanoate, t-butyl peroxypivalate, 1, 3-tetramethylbutyl peroxy2-ethylhexanoate, t-amyl peroxy2-ethylhexanoate, t-butyl peroxy2-ethylhexanoate, t-amyl peroxy3, 5-trimethylhexanoate, t-butyl peroxy3, 5-trimethylhexanoate, t-amyl peroxybenzoate and the like; peroxycarbonates such as di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxyisopropylcarbonate, and 1, 6-bis (tert-butylperoxycarbonyloxy) hexane; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroctoate, lauroyl peroxide, etc.; azo compounds such as azobisisobutyronitrile, 4 '-azobis (4-cyanovaleric acid), 2' -azobis (2, 4-dimethylvaleronitrile), and the like, but the curing accelerator is not particularly limited thereto. Preferred are ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketones, alkyl peresters, and percarbonates, and more preferred are dialkyl peroxides. The amount of the radical polymerization initiator to be added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the curable resin composition. When the amount of the radical polymerization initiator used is large, there is a possibility that the molecular weight may not be sufficiently increased at the time of polymerization.
The curable resin composition of the present invention may contain an epoxy resin. As the epoxy resin, any of conventionally known epoxy resins can be used. Specific examples of the epoxy resin 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, glycidyl ether-based epoxy resins obtained by glycidylating alcohols and the like, alicyclic epoxy resins typified by 4-vinyl-1-cyclohexene diepoxide, 3,4' -epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester and the like, glycidyl amine-based epoxy resins typified by tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidyl-p-aminophenol and the like, glycidyl ester-based epoxy resins and the like, but are not limited thereto. These may be used alone or in combination of two or more.
In addition, a phenol aralkyl resin obtained by condensation reaction of a phenol and a bishalomethyl aralkyl derivative or an aralkyl alcohol derivative is particularly preferable as a raw material, and an epoxy resin obtained by dehydrochlorination reaction of the phenol aralkyl resin and epichlorohydrin is preferable as an epoxy resin because of its low hygroscopicity, flame retardancy, and excellent dielectric characteristics.
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) may be blended as necessary.
As the epoxy resin curing agent, an amine compound, an acid anhydride compound, an amide compound, a phenol compound, an active ester resin, or the like can be used. Specific examples of the curing agent that can be used include: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, polycondensates of 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 dimethylol groups, bisphenols and their modified products, imidazole, BF 3 Amine complexes, guanidine derivatives, etc.
When an active ester resin is used as the curing agent, compounds having two or more ester groups having high reactivity in one molecule, such as phenol esters, thiophene esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are preferable. The active ester curing agent is preferably obtained by a condensation reaction of at least one compound selected from a carboxylic acid compound and a thiocarboxylic acid compound with at least one compound selected from a hydroxyl 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 hydroxyl compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and at least one compound selected from a phenol compound and a naphthol compound is preferable.
The amount of the epoxy resin curing agent used is preferably 0.5 to 1.5 equivalents, and particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group (or glycidyl group). When the amount of the epoxy resin curing agent used is less than 0.5 equivalent or more than 1.5 equivalent to 1 equivalent of the epoxy group, curing is incomplete and good cured properties may not be obtained.
Examples of the catalyst (curing accelerator) for curing the epoxy resin include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5.4.0) undec-7-ene, tris (dimethylaminomethyl) phenol, and benzyldimethylamine; phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine. The amount of the curing catalyst to be blended is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the total amount of the curable resin composition.
The curable resin composition of the present invention may contain a cyanate resin. As the cyanate ester compound that can be incorporated into the curable resin composition of the present invention, conventionally known cyanate ester compounds can be used. Specific examples of the cyanate ester compound include: cyanate ester compounds obtained by reacting cyanogen halide such as polycondensates of phenols with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with ketones, and polycondensates of bisphenols with various aldehydes are not limited to these compounds. 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, dihydroxynaphthalene, and the like.
As the various aldehydes, there may be mentioned: formaldehyde, acetaldehyde, alkylaldehydes, benzaldehyde, alkyl-substituted benzaldehydes, hydroxybenzaldehydes, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde and the like.
Examples of the various diene compounds include: dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene and the like.
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
Specific examples of the cyanate ester compound include: dicyanobenzene, tricyanobenzene, dicyanonacylnaphthalene, dicyanonacylbiphenyl, 2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) methane, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2' -bis (3, 5-dimethyl-4-cyanatophenyl) propane, 2' -bis (4-cyanatophenyl) ethane, 2' -bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) sulfide, phenol novolak cyanate ester, a compound obtained by converting the hydroxyl group of phenol-dicyclopentadiene cocondensate into a cyanate group, and the like, but are not limited thereto.
In addition, a cyanate ester compound which is described in japanese patent application laid-open No. 2005-264154 as a synthetic method is particularly preferable because of its low hygroscopicity, flame retardancy, and excellent dielectric characteristics.
When the curable resin composition of the present invention contains a cyanate ester resin, a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate, or the like may be contained in the curable resin composition of the present invention in order to trimerize the cyanate group to form an s-triazine ring as necessary. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the total mass of the curable resin composition.
In addition, if necessary, a powder such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, or glass powder, or an inorganic filler obtained by pulverizing or forming the powder into a spherical shape may be added to the curable resin composition of the present invention. In particular, when a curable resin composition for sealing a semiconductor is obtained, the amount of the inorganic filler used in the curable resin composition is usually in the range of 80 to 92% by mass, and preferably in the range of 83 to 90% by mass.
The curable resin composition of the present invention may contain known additives as needed. Specific examples of additives that can be used include: polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, surface treatment agents for filling materials such as polyphenylene ether, polystyrene, polyethylene, polyimide, fluorine-containing resins, silicone gel, silicone oil, silane coupling agents, and release agents; colorants such as carbon black, phthalocyanine blue and phthalocyanine green. The amount of these additives is preferably 1000 parts by mass or less, and more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.
The curable resin composition of the present invention can be prepared into a varnish-like composition (hereinafter, simply referred to as a varnish) by adding an organic solvent. The addition of the solvent reduces the viscosity during the preparation of the curable resin composition, and tends to improve the handleability and further improve the impregnation into a base material such as glass cloth. Examples of the solvent to be used include: amide solvents such as γ -butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and N, N-dimethylimidazolidinone; sulfones such as sulfolane; ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl 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 toluene and xylene. In addition, when the boiling point of the solvent used in the production of the laminate is too high, the solvent may remain as a residual solvent. The boiling point of the solvent used is preferably 200 ℃ or lower, more preferably 180 ℃ or lower. The solvent is used in a range of a solid content concentration excluding the solvent in the varnish obtained, 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, any known reaction capable of reacting with an unsaturated double bond can be applied. Examples thereof include radical polymerization, ene reaction, diels-Alder reaction and the like. When curing is performed by using these reactions, unlike a curing reaction utilizing a ring-opening reaction of an epoxy group, a polar group is not generated during curing, and therefore, deterioration of water absorption and electrical characteristics due to improvement of heat resistance can be reduced.
In the curable resin composition of the present invention, a compound containing an optional alkenyl group may be contained in the composition. In curing, radical polymerization based on a combination of the alkenyl compound described in the present invention and an optional alkenyl group-containing compound may be utilized. Any alkenyl group may be a substituted or unsubstituted straight-chain, branched or cyclic alkenyl group, and any alkenyl group is not particularly limited as long as it is a known alkenyl group, and preferable specific examples thereof include: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl, cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, cyclononadecenyl, cycloeicosenylAnd polycyclic compounds such as norbornyl are also included in the scope. Further, as an optional alkenyl group, C is more preferable 6 ～C 20 1 to 4 ring alkenyl groups of (a). In addition, any number of hydrogen atoms in any alkenyl group may each be substituted with a halogen atom; substituted or unsubstituted straight, branched or cyclic alkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted straight, branched or cyclic alkenyl; hydroxyl, alkoxy, amino, cyano, carbonyl, carboxyl and ester group.
The method for producing the curable resin composition of the present invention can be carried out according to a known method, but is not limited thereto. For example, the components may be mixed only homogeneously, or a prepolymer may be formed. Specifically, the prepolymer is formed by heating the alkenyl group-containing compound represented by the above formula (1) and the maleimide resin in the presence or absence of a catalyst, 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 may be added to the alkenyl group-containing compound and the maleimide resin represented by the above formula (1) as necessary to form a prepolymer. For the mixing of the components or the formation of the prepolymer, for example, an extruder, a kneader, a roll or the like is used in the absence of a solvent, and a reaction vessel with a stirring device is used in the presence of a solvent.
The curable resin composition of the present invention is obtained by, for example, uniformly mixing the above components at a predetermined ratio. Further, for example, the curable resin composition of the present invention is usually pre-cured at 130 to 180 ℃ for 30 to 500 seconds and then post-cured at 150 to 200 ℃ for 2 to 15 hours to perform a sufficient curing reaction, thereby obtaining a cured product of the present invention. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and the solvent may be removed and then cured.
The cured product of the curable resin composition of the present invention obtained in this manner 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 where moisture resistance, heat resistance, and high adhesiveness are required. Specifically, the resin composition is useful as a material for all electric and electronic parts such as an insulating material, a laminate (printed circuit board, BGA substrate, laminate substrate, etc.), a sealing material, and a resist. In addition, the resin composition can be used in the fields of molding materials, composite materials, coating materials, adhesives, and the like. Particularly in semiconductor sealing, is a material having an advantageous reflow resistance.
The semiconductor device has a structure obtained by sealing with the curable resin composition of the present invention. Examples of the semiconductor device 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), TQFP (thin 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. 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 fibers of inorganic substances other than glass, poly (paraphenylene terephthalamide) (Kevlar (registered trademark), manufactured by dupont), wholly aromatic polyamide, and polyester; and poly-p-phenylene benzobis
Organic fibers such as azole, polyimide, and carbon fiber, but not particularly limited thereto. The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, and chopped strand mat. As a weaving method of the woven fabric, a plain weaving method, a herringbone weaving method, a twill weaving method, and the like are known, and these known methods can be appropriately selected and used according to the intended use and performance. In addition, it is preferable to useThe woven fabric obtained by opening the woven fabric and the glass woven fabric obtained by surface treatment with a silane coupling agent or the like are used. The thickness of the substrate is not particularly limited, and is preferably about 0.01mm to about 0.4mm.
The prepreg is cut into a desired shape, laminated with a copper foil or the like as needed, and then the laminate is subjected to pressure application by a press molding method, an autoclave molding method, a sheet winding molding method or the like, and the curable resin composition is cured by heating, whereby a laminate (printed circuit board) for electric and electronic use and a carbon fiber reinforced material can be obtained.
Examples
The present invention will be described in more detail below with reference to examples. It should be noted that the present invention is not limited to these examples. In the examples, the physical properties were measured under the following conditions.
< melting Point >
Measured by DSC. The value of the endothermic peak top was taken as the melting point.
The device comprises the following steps: manufactured by Q-2000 TA-instruments
Mode (2): m (modulation) DSC mode
Temperature rise rate: 10 deg.C/min
Measurement temperature range: 30-300 DEG C
< 1 H-NMR>
The device comprises the following steps: JNM-ECS400 manufactured by Nippon electronics Co., ltd
(example 1)
In a flask equipped with a thermometer, a condenser and a 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 and 67.6 parts by mass of potassium carbonate were charged, and the internal temperature was raised to 100 ℃. The reaction was carried out at 100 ℃ for 6 hours, allowed to cool naturally, and then 200 parts by mass of toluene was added, washed with water, and concentrated under reduced pressure, whereby 37.9 parts by mass (yield 98%) of an etherification reaction product (AP-CC) of cyanuric chloride represented by the following formula (4) with 2-allylphenol was obtained. The melting point of the obtained reaction product was 110 ℃.
(example 2)
In a flask equipped with a thermometer, a condenser and a stirrer, 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 82.9 parts by mass of potassium carbonate were charged, and the internal temperature was raised to 100 ℃. The reaction was carried out at 100 ℃ for 6 hours, allowed to cool naturally, and then 200 parts by mass of toluene was added, washed with water, and concentrated under reduced pressure, whereby 39.2 parts by mass (yield 82%) of an etherification reaction product (PP-CC) of cyanuric chloride represented by the following formula (5) with 2- (1-propenyl) phenol was obtained.
The melting point of the obtained reaction product was 131 ℃.
(example 3)
In 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 charged and stirred, and the internal temperature was raised to 30 ℃. 12.6 parts by mass of sodium hydroxide was added over 1.5 hours, and the reaction was carried out at 30 ℃ for 6 hours. Acetone was removed by concentration under reduced pressure, and then 100g of toluene was added, washed with water, and concentrated under reduced pressure, whereby 47.6 parts by mass (yield 84%) of an etherification reaction product (Eu-CC) of cyanuric chloride represented by the following formula (6) with eugenol was obtained. The melting point of the reaction product obtained is 125 ℃.
(example 4)
A flask equipped with a thermometer, a condenser and a stirrer was charged with 40.3 parts by mass of 2-allylphenol, 117 parts by mass of dimethyl sulfoxide and 58.8 parts by mass ofAnd stirring was started. 24.6g of sodium hydroxide were added portionwise over 1 hour and the internal temperature was raised to 70 ℃. 26.3 parts by mass of 1, 4-bis (chloromethyl) benzene were added over 1 hour, and the reaction was carried out at 70 ℃ for 2 hours. The crystals deposited were naturally cooled and then filtered off by filtration to obtain 49.1 parts by mass (yield 88%) of an etherification reaction product (AP-XLC) of 1, 4-bis (chloromethyl) benzene and 2-allylphenol represented by the following formula (7). The melting point of the obtained reaction product was 46 ℃. Will be measured 1 The H-NMR chart is shown in FIG. 1.
1 H-NMR(400MHz，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)
In a flask equipped with a thermometer, a condenser and a stirrer, 40.3 parts by mass of 2- (1-propenyl) phenol, 117 parts by mass of dimethyl sulfoxide and 58.8 parts by mass of water were charged and stirring was started. 24.6g of sodium hydroxide were added portionwise over 1 hour and the internal temperature was raised to 70 ℃. 26.3 parts by mass of 1, 4-bis (chloromethyl) benzene were added over 1 hour, and the reaction was carried out at 70 ℃ for 2 hours. The crystals deposited were naturally cooled and then filtered off by filtration to obtain 49.0 parts by mass (yield 88%) of an etherification reaction product (PP-XLC) of 1, 4-bis (chloromethyl) benzene and 2- (1-propenyl) phenol represented by the following formula (8). The melting point of the reaction product obtained was 53 ℃. Will be determined 1 The H-NMR is shown in FIG. 2.
1 H-NMR(400MHz，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 thermometer is arranged on,In a flask equipped with a condenser and a stirrer, 35.0 parts by mass of 1, 4-bis (chloromethyl) benzene, 65.7 parts by mass of eugenol, 66.3 parts by mass of potassium carbonate, and 210mL of dimethylformamide were charged, and the mixture was reacted at room temperature for 6 hours, and then heated to 70 ℃ and reacted for 6 hours. 500 parts by mass of water was added to precipitate an isomer, which was separated by filtration. The filtered solid was washed with a large amount of water, then with a large amount of methanol, and dried at 80 ℃ for 12 hours, whereby 78.6 parts by mass (yield 91%) of an etherification reaction product of 1, 4-bis (chloromethyl) benzene represented by the following formula (9) with eugenol (Eu-XLC) was obtained. The melting point of the obtained reaction product was 106 ℃. Will be determined 1 The H-NMR chart is shown in FIG. 3.
1 H-NMR(400MHz，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)
In a flask equipped with a thermometer, a condenser and a stirrer, 35.0 parts by mass of 1, 4-bis (chloromethyl) benzene, 65.7 parts by mass of isoeugenol, 66.3 parts by mass of potassium carbonate and 210mL of dimethylformamide were charged, reacted at room temperature for 6 hours, and then heated to 70 ℃ and reacted for 6 hours. 500 parts by mass of water was added to precipitate a solid, which was separated by filtration. The filtered solid was washed with a large amount of water, then with a large amount of methanol, and dried at 80 ℃ for 12 hours, whereby 76.0 parts by mass (yield 88%) of an etherification reaction product (IEu-XLC) of 1, 4-bis (chloromethyl) benzene and isoeugenol represented by the following formula (10) was obtained. The melting point of the resulting reaction product was 145.8 ℃.
(example 8)
At the installation of a thermometer40.3 parts by mass of 2-allylphenol, 230 parts by mass of dimethyl sulfoxide, and 58.8 parts by mass of water were charged into a flask equipped with a condenser and a stirrer, and stirring was started. 24.6g of sodium hydroxide were added portionwise over 1 hour and the internal temperature was raised to 70 ℃. 37.7 parts by mass of p-bis (chloromethyl) biphenyl were added over 1 hour, and the reaction was carried out at 70 ℃ for 2 hours. The precipitated crystals were filtered off by filtration, whereby 60.9 parts by mass (yield 91%) of an etherification reaction product of p-bis (chloromethyl) biphenyl and 2-allylphenol (AP-BCMB) represented by the following formula (11) was obtained. The melting point of the obtained reaction product was 105 ℃. Will be measured 1 The H-NMR chart is shown in FIG. 4.
1 H-NMR(400MHz，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)
In 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 charged and stirring was started. 12.3g of sodium hydroxide are added portionwise over 1 hour and the internal temperature is raised to 70 ℃. 18.8 parts by mass of p-bis (chloromethyl) biphenyl were added over 1 hour, and the reaction was carried out at 70 ℃ for 2 hours. The precipitated crystals were filtered off by filtration, whereby 31.3 parts by mass (yield 93%) of an etherification reaction product of p-bis (chloromethyl) biphenyl and 2- (1-propenyl) phenol (PP-BCMB) represented by the following formula (12) was obtained. The melting point of the resulting reaction product was 164 ℃. Will be measured 1 H-NMR is shown in FIG. 5.
1 H-NMR(400MHz，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)
In a flask equipped with a thermometer, a condenser and a stirrer, 24.6 parts by mass of eugenol, 250 parts by mass of dimethyl sulfoxide and 29.4 parts by mass of water were charged, and stirring was started. 12.3g of sodium hydroxide are added portionwise over 1 hour and the internal temperature is raised to 70 ℃. 18.8 parts by mass of p-bis (chloromethyl) biphenyl were added over 1 hour, and the reaction was carried out at 70 ℃ for 2 hours. The precipitated crystals were filtered off by filtration, whereby 31.9 parts by mass (yield 84%) of an etherification reaction product of p-bis (chloromethyl) biphenyl and eugenol represented by the following formula (13) (Eu-BCMB) was obtained. The melting point of the obtained reaction product was 102 ℃.
(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 mixed in the proportions (parts by weight) shown in Table 1, heated and melt-mixed in a metal container, directly poured into a mold and cured at 220 ℃ for 2 hours.
In comparative example 1, an epoxy resin, a maleimide resin and the like were blended at the ratio (parts by weight) shown in table 1, kneaded by a mixing roll, tabletted, and then transfer-molded to prepare a resin molded body, which was cured at 200 ℃ for 2 hours and further at 220 ℃ for 6 hours.
The physical properties of the cured product obtained in the above manner were measured for the following items, and the obtained results are shown in table 1.
< Heat resistance test >
Glass transition temperature: the glass transition temperature is measured by a dynamic viscoelasticity tester and is a temperature at which tan δ is a maximum value.
A measuring device: manufactured by TA-instruments, Q-800
Measurement temperature range: 30-350 DEG C
Temperature rise rate: 2 ℃ per minute
Test piece size: 5mm × 50mm × 0.8mm
< dielectric constant test, dielectric loss tangent test >
The 1GHz resonator manufactured by Kanto electronic applications development was used and tested by the resonator perturbation method. Wherein the test was conducted under the conditions that the sample size was 1.7mm in width by 100mm in length and 1.7mm in thickness.
BMI:4,4' -bismaleimidodiphenylmethane (manufactured by Tokyo chemical industry Co., ltd.)
MIR: maleimide resin described in example 4 of Japanese patent laid-open publication No. 2009-001783
Epoxy resin: NC-3000-L (manufactured by Nippon chemical Co., ltd.)
Phenolic resin: GPH-65 (manufactured by Nippon chemical Co., ltd.)
2E-4MZ: 2-Ethyl-4-methylimidazole (manufactured by Tokyo chemical industry Co., ltd.)
DCP: dicumyl peroxide (Kayaku Akzo Co., ltd.)
From the results of table 1, it was confirmed that: examples 11 to 19 using the alkenyl group-containing compound of the present invention had excellent dielectric characteristics and high heat resistance.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
It is to be noted that the present application is based on two japanese patent applications (japanese patent application 2018-74454, japanese patent application 2018-74456) applied on 9/4/2018, the entire contents of which are incorporated by reference. In addition, all references cited herein are incorporated by reference in their entirety.
Industrial applicability
Therefore, the alkenyl group-containing compound of the present invention is useful for various composite materials such as insulating materials for electric and electronic parts (highly reliable semiconductor sealing materials and the like), laminated boards (printed wiring boards, substrates for BGA, laminated boards and the like), adhesives (conductive adhesives and the like), CFRP, and coatings.
Claims (4)
1. An alkenyl-containing compound represented by the following formula (1),
in formula (1), X is represented by the following formula (2-2); y represents an alkenyl group, and when a plurality of Y are present, the plurality of Y 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 a plurality of Z are present, the plurality of Z may be the same or different; l represents a natural number of 1 to 6; m and n are each an integer of 0 or more, m + n =1 to 5 is satisfied, and at least one of the l m present is 1 or more,
in formula (2-2), represents bonding to the oxygen atom in formula (1).
2. 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.
4. A cured product obtained by curing the curable resin composition according to claim 2 or 3.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018074454 | 2018-04-09 | ||
| JP2018074456 | 2018-04-09 | ||
| JP2018-074456 | 2018-04-09 | ||
| JP2018-074454 | 2018-04-09 | ||
| PCT/JP2019/014919 WO2019198606A1 (en) | 2018-04-09 | 2019-04-04 | Alkenyl-group-containing compound, curable resin composition, and cured object obtained therefrom |
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| CN111918889A CN111918889A (en) | 2020-11-10 |
| CN111918889B true CN111918889B (en) | 2022-12-20 |
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| Country | Link |
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| JP (1) | JP7153994B2 (en) |
| KR (1) | KR20200141982A (en) |
| CN (1) | CN111918889B (en) |
| WO (1) | WO2019198606A1 (en) |
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| CN112341787B (en) * | 2020-11-30 | 2022-09-20 | 南亚新材料科技股份有限公司 | Bio-based resin composition, metal foil-clad laminate, and printed wiring board |
| TW202330717A (en) * | 2021-09-21 | 2023-08-01 | 日商日產化學股份有限公司 | Non-photosensitive insulation film-forming composition |
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| JPS62109810A (en) * | 1985-11-06 | 1987-05-21 | Sumitomo Chem Co Ltd | Thermosetting resin composition |
| JPS6377986A (en) * | 1986-09-19 | 1988-04-08 | Sumitomo Chem Co Ltd | Sealing resin composition |
| US4808717A (en) * | 1986-09-17 | 1989-02-28 | Sumitomo Chemical Company, Limited | Thermosetting resin composition |
| JPH01144410A (en) * | 1987-08-17 | 1989-06-06 | Hercules Inc | Thermosetting resin composition |
| EP0469684A1 (en) * | 1990-07-30 | 1992-02-05 | Shell Internationale Researchmaatschappij B.V. | Polyimide compositions |
| US5095074A (en) * | 1987-08-17 | 1992-03-10 | Hercules Incorporated | Thermosettable resin compositions |
| JPH04330066A (en) * | 1990-11-26 | 1992-11-18 | Toagosei Chem Ind Co Ltd | S-triazine compound |
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|---|---|---|---|---|
| JP2570923B2 (en) | 1991-06-07 | 1997-01-16 | 信越化学工業株式会社 | Thermosetting resin composition |
| GB2511574B (en) | 2013-03-08 | 2017-10-04 | Magnomatics Ltd | Permanent magnet assembly for mounting to a rotor |
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2019
- 2019-04-04 WO PCT/JP2019/014919 patent/WO2019198606A1/en active Application Filing
- 2019-04-04 KR KR1020207025334A patent/KR20200141982A/en not_active Application Discontinuation
- 2019-04-04 CN CN201980020008.5A patent/CN111918889B/en active Active
- 2019-04-04 JP JP2020513229A patent/JP7153994B2/en active Active
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Also Published As
| Publication number | Publication date |
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| WO2019198606A1 (en) | 2019-10-17 |
| KR20200141982A (en) | 2020-12-21 |
| JP7153994B2 (en) | 2022-10-17 |
| CN111918889A (en) | 2020-11-10 |
| JPWO2019198606A1 (en) | 2021-05-13 |
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