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WO2023276760A1 - Composé éther d'allyle, composition de résine associée, produit durci associé et procédé de production d'un composé éther d'allyle - Google Patents

Composé éther d'allyle, composition de résine associée, produit durci associé et procédé de production d'un composé éther d'allyle Download PDF

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WO2023276760A1
WO2023276760A1 PCT/JP2022/024563 JP2022024563W WO2023276760A1 WO 2023276760 A1 WO2023276760 A1 WO 2023276760A1 JP 2022024563 W JP2022024563 W JP 2022024563W WO 2023276760 A1 WO2023276760 A1 WO 2023276760A1
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formula
resin
group
allyl ether
ether compound
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Japanese (ja)
Inventor
正浩 宗
一男 石原
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention provides an allyl ether compound that provides a cured product excellent in low dielectric properties, high heat resistance, etc., a resin composition containing the allyl ether compound as an essential component, and a cured product and encapsulant obtained from this resin composition. , a circuit board material, a prepreg or a laminate, and a method for producing an allyl ether compound.
  • Thermosetting resins such as epoxy resins and phenolic resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. It is used in a wide variety of materials. In particular, it is widely used for printed wiring boards, which is one of electrical and electronic materials, by imparting flame retardancy to epoxy resins.
  • Patent Document 1 discloses a method of using an imide group-containing phenolic resin to improve heat resistance and mechanical properties more than epoxy resins, and the heat resistance is improved by containing an imide group. .
  • Patent Document 4 a compound obtained by epoxidizing an imide group-containing phenolic resin is exemplified.
  • Patent Document 5 discloses a composition in which the heat resistance and flame retardancy of a substrate is improved by using a maleimide compound, an epoxy resin, and a phenolic curing agent with a specific structure
  • Patent Documents 6 and 7 disclose a composition having a specific structure.
  • Patent Document 8 exemplifies that a curable resin composition having low dielectric properties and high heat resistance can be obtained by using a maleimide compound and an allyl ether compound.
  • Patent Document 9 discloses that a composition having excellent curability and heat resistance can be obtained by using a thermosetting resin composition containing a maleimide compound having a specific structure and a compound having an allyl group or a methallyl group. exemplified.
  • none of the curable resin compositions disclosed in any of the documents sufficiently satisfies the requirements for dielectric properties based on recent advances in functionality, and does not satisfy all physical properties at the same time.
  • the problem to be solved by the present invention is to provide a resin composition and a cured product thereof that have excellent performance satisfying both low dielectric properties and high heat resistance and are useful for applications such as lamination, molding, and adhesion. It is something to do.
  • the present invention is an allyl ether compound (resin) characterized by being represented by the following general formula (1).
  • R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R2 independently represents a hydrogen atom, a group represented by formula (2), or a group represented by formula (3), at least one of which is represented by formula (2) or formula (3).
  • R 3 independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
  • R 4 independently represents a hydrogen atom or a group represented by formula (2)
  • R 9 independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • A is a residue obtained by removing two R 2 from formula (1), and R 2 in the residue is independently a hydrogen atom or a group represented by formula (2).
  • Me represents a methyl group.
  • i is an integer from 0 to 2; n and p1 each indicate the number of repetitions, and the average value is a number from 0 to 5.
  • R 1 is preferably a methyl group or a phenyl group, and i is preferably 1 or 2.
  • the present invention also provides an allyl ether compound obtained by allyl-etherifying a polyhydric hydroxy resin represented by the following general formula (4).
  • R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R 2 ′ independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), at least one of which is represented by formula (5) or formula (6).
  • R 3 independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
  • R 4 independently represents a hydrogen atom or a group represented by formula (5).
  • A' is a residue obtained by removing two R2 ' from formula (4), and R2 ' in the residue is independently a hydrogen atom or a group represented by formula (5).
  • Me represents a methyl group.
  • i is an integer from 0 to 2;
  • m and p2 each indicate the number of repetitions, and the average value is a number from 0 to 5.
  • the present invention also provides a resin composition characterized by containing the allyl ether compound and the maleimide compound.
  • the present invention also provides a cured product obtained by curing the above resin composition, and a circuit board material, encapsulating material, prepreg, or laminate using the above resin composition.
  • the present invention also provides a method for producing the above allyl ether compound, characterized by subjecting the above polyhydric hydroxy resin to allyl etherification to obtain the above allyl ether compound.
  • allyl ether compound (resin) of the present invention With the allyl ether compound (resin) of the present invention, a cured product with a high glass transition temperature can be obtained as the resin composition. It also has excellent dielectric properties, and exhibits good properties in laminates and electronic circuit boards that require a low dielectric constant and low dielectric loss tangent.
  • FIG. 1 is a GPC chart of an allyl ether compound obtained in Example 1.
  • FIG. 1 is an IR chart of an allyl ether compound obtained in Example 1.
  • FIG. 1 is an IR chart of an allyl ether compound obtained in Example 1.
  • the allyl ether compound of the present invention is an allyl ether compound represented by general formula (1).
  • polyhydric hydroxy compound resin
  • n polyhydric hydroxy compound represented by the above general formula (4)
  • n 0 (monomer)
  • n 1 (two polymer)
  • common symbols have the same meanings.
  • R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms. , or allyl groups are preferred.
  • the alkyl group may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, cyclohexyl, methyl A cyclohexyl group and the like can be mentioned.
  • Aryl groups include phenyl, tolyl, xylyl, and ethylphenyl groups.
  • the aralkyl group includes benzyl group, ⁇ -methylbenzyl group and the like. Among these substituents, a phenyl group and an alkyl group having 1 to 3 carbon atoms are preferable, and a methyl group is particularly preferable, from the viewpoints of availability and reactivity when a cured product is obtained.
  • the substitution position of R 1 may be ortho-position, meta-position or para-position with respect to the allyl ether group, but ortho-position is preferred.
  • R 2 represents a hydrogen atom or a group represented by formula (2) or formula (3), at least one of which is represented by formula (2) or formula (3). Unlike R 1 which is a substituent, R 2 does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • the group represented by the formula (2) is a group derived from an aromatic monovinyl compound represented by the following general formula (8a) among raw aromatic vinyl compounds for the polyhydric hydroxy resin represented by the general formula (4).
  • the group represented by formula (3) is a group derived from an aromatic divinyl compound represented by general formula (8b) among aromatic vinyl compounds.
  • R 9 independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • a hydrogen atom or an alkyl group is preferred.
  • i is the number of substitutions and is 0 to 2, preferably 1 or 2, more preferably 2;
  • n is the number of repetitions and represents a number of 0 or more, the average value (number average) is 0 to 5, preferably 1.0 to 4.0, more preferably 1.1 to 3.0, 1.2 to 2.5 are more preferred.
  • R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms are the same as those for R 1 . Similarly to R 2 , unlike R 1 which is a substituent, R 3 does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • R 3 is the availability and heat resistance of the cured product. From a viewpoint, a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom and an ethyl group are particularly preferable.
  • a vinyl group may be included as R3. Further , the substitution position of R3 may be ortho-position, meta-position or para-position, but meta-position and para-position are preferred. Preferably one of R3 is an ethyl group and the rest are hydrogen atoms.
  • A is a residue obtained by removing two R 2 from formula (1), and R 2 in the residue is a hydrogen atom or a group represented by formula (2).
  • A is a divalent group having a structure similar to that of general formula (1), but does not become a group represented by formula (3).
  • R3 has the same definition as in formula ( 2 ).
  • R4 represents a hydrogen atom or a group represented by formula (2).
  • R 4 does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • p1 is the number of repetitions and represents a number of 0 or more, and its average value (number average) is 0 to 5, preferably 0.01 to 3, more preferably 0.1 to 2.0, and 0.01 to 3.0. 2 to 1.0 is more preferred, and 0.3 to 0.8 is particularly preferred.
  • the weight average molecular weight (Mw) of the allyl ether compound (resin) of the present invention is preferably 400-5000, more preferably 500-4500, even more preferably 600-4000.
  • the number average molecular weight (Mn) is preferably from 350 to 2,000, more preferably from 400 to 1,500, even more preferably from 450 to 1,000.
  • the phenolic hydroxyl equivalent (g/eq.) is preferably 5,000 or more, more preferably 10,000 or more. When it exceeds 10,000, it exceeds the amount of hydroxyl groups that can be measured substantially, indicating that the phenolic hydroxyl groups of the starting polyhydric hydroxy resin are almost completely allyl-etherified.
  • the softening point is preferably 40 to 180°C, more preferably 50 to 120°C.
  • a polyhydric hydroxy resin which is a raw material for the allyl ether compound (resin) of the present invention, is represented by general formula (4).
  • R 2 ' independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), and at least one represents formula (5) or formula ( 6).
  • R 4 independently represents a hydrogen atom or a group represented by formula (5).
  • A' is a residue obtained by removing two R2 ' from formula (4), and R2 ' in the residue is independently a hydrogen atom or a group represented by formula (5).
  • R 1 and i have the same definitions as in general formula (1).
  • the definition of m is the same as that of n in the general formula (1), and is almost the same even in the case of the relationship between raw materials and products.
  • R 2 ' represents a hydrogen atom or a group represented by formula (5) or formula (6), at least one of which is represented by formula (5) or formula (6).
  • R 2 ' like R 2 in general formula (1), does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • R3 has the same definition as in formula ( 2 ).
  • R 3 , R 4 and Me have the same definitions as in formula (3).
  • p2 has the same meaning as p1 in formula (3), it is almost the same even in the case of the relationship between raw materials and products.
  • A' is a residue obtained by removing two R2 ' from formula (4), and R2 ' in the residue is a hydrogen atom or a group represented by formula (5).
  • A' is a divalent group having a structure similar to that of general formula (4), but is not a group represented by formula (6).
  • the weight average molecular weight (Mw) of the polyhydric hydroxy resin represented by formula (4) is preferably 400-5000, more preferably 500-3000, even more preferably 600-2000.
  • the number average molecular weight (Mn) is preferably from 350 to 2,000, more preferably from 400 to 1,500, even more preferably from 450 to 1,000.
  • the phenolic hydroxyl group equivalent (g/eq.) is preferably 190-500, more preferably 220-400, even more preferably 250-350.
  • the softening point is preferably 50 to 180°C, more preferably 50 to 120°C.
  • the polyhydric hydroxy resin represented by the general formula (4) is obtained by reacting the dicyclopentadiene type polyhydric hydroxy resin (a) represented by the following general formula (7) in the presence of an acid catalyst with the general formula ( It is obtained by reacting an aromatic monovinyl compound represented by 8a) and/or an aromatic divinyl compound represented by general formula (8b). Aromatic monovinyl compounds and aromatic divinyl compounds are collectively referred to as aromatic vinyl compounds.
  • the polyhydric hydroxy resin (a) has a structure in which phenols are linked by dicyclopentadiene.
  • R 1 and i have the same definitions as in general formula (1), and s has the same definition as n in general formula (1), but in the case of the relationship between raw materials and products are almost the same.
  • R3 has the same definition as in formula ( 2 ).
  • the substitution position may be ortho, meta or para with respect to the vinyl group, preferably meta and para.
  • the substitution position of another vinyl group with respect to the vinyl group may be any of the ortho position, meta position, and para position. and para positions are preferred, and mixtures thereof may also be used.
  • the aromatic vinyl compound used as a raw material essentially comprises an aromatic monovinyl compound (compound represented by general formula (8a)) and contains an aromatic divinyl compound (compound represented by general formula (8b)). good too.
  • the compounding amount may be adjusted while considering the molecular weight of the polyhydric hydroxy resin (a) so as to obtain the desired molecular weight.
  • An aromatic monovinyl compound becomes a substituent represented by the formula (2) through an addition reaction, and exhibits an effect of reducing dielectric properties.
  • aromatic monovinyl compounds examples include vinyl aromatic compounds such as styrene, vinylnaphthalene, vinylbiphenyl and ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and o,p-dimethylstyrene.
  • o-ethylvinylbenzene m-ethylvinylbenzene, p-ethylvinylbenzene, ethylvinylbiphenyl, and ethylvinylnaphthalene
  • cyclic vinyl aromatic compounds such as indene, acenaphthylene, benzothiophene, and coumarone. group compounds and the like.
  • Styrene and ethylvinylbenzene are preferred. These can be used singly or in combination of two or more.
  • aromatic divinyl compounds include divinyl aromatic compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Divinylbenzene is preferred. These can be used singly or in combination of two or more.
  • the blending amount of the aromatic monovinyl compound and the aromatic divinyl compound is preferably 15 to 50% by mass of the aromatic monovinyl compound and 50 to 85% by mass of the aromatic divinyl compound relative to the total amount of the aromatic vinyl compound. .
  • the aromatic monovinyl compound is preferably 15-50% by mass, more preferably 17-45% by mass.
  • the aromatic divinyl compound is preferably 50-85% by weight, more preferably 55-83% by weight.
  • the phenolic hydroxyl group equivalent (g/eq.) of the polyhydric hydroxy resin (a) represented by the general formula (7) is preferably 160-220, more preferably 165-210, even more preferably 170-200.
  • the polyhydric hydroxy resin (a) represented by the general formula (7) is obtained by reacting a phenol represented by the following general formula (9) with dicyclopentadiene in the presence of a Lewis acid.
  • R 1 and i have the same definitions as in general formula (1).
  • the substitution position of R 1 may be ortho-position, meta-position or para-position, but ortho-position is preferred.
  • the structural formula of dicyclopentadiene is as follows.
  • Phenols represented by general formula (9) include phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, tolylphenol, benzylphenol, ⁇ -methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, ditolylphenol , dibenzylphenol, bis( ⁇ -methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methylisopropylphenol, methylbutylphenol, methyl-t-butylphenol, methylallylphenol, tolylphenylphenol and the like. Phenol, cre
  • the catalyst used in the above reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, and the like.
  • boron trifluoride-ether complex is preferable because of ease of handling.
  • the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene.
  • the amount of dicyclopentadiene used is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, still more preferably 1 mol of phenols. 0.10 to 0.40 mol, particularly preferably 0.10 to 0.20 mol.
  • the phenol and the catalyst are charged in a reactor, and dicyclopentadiene is added dropwise over 0.1 to 10 hours, preferably 0.5 to 8 hours, more preferably 1 to 6 hours. .
  • the reaction temperature is preferably 50-200°C, more preferably 100-180°C, even more preferably 120-160°C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, even more preferably 4 to 8 hours.
  • an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst.
  • solvents such as aromatic hydrocarbons such as toluene and xylene and ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve and washed with water.
  • a polyhydric hydroxy resin represented by formula (7) can be obtained.
  • aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethylene glycol dimethyl ether, Solvents such as ethers such as diethylene glycol dimethyl ether may also be used.
  • a predetermined aromatic vinyl compound is added to the polyhydric hydroxy resin (a). It is a method of reacting at a ratio of The reaction ratio is 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, more preferably 0.15, of the aromatic vinyl compound per 1 mol of the phenolic hydroxyl group of the polyhydric hydroxy resin (a). ⁇ 0.95 mol is particularly preferred.
  • the catalyst used in the reaction is an acid catalyst, specifically mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid and p-toluenesulfonic acid; Examples include Lewis acids such as aluminum, iron chloride and boron trifluoride, and solid acids such as activated clay, silica-alumina and zeolite. Among them, p-toluenesulfonic acid is preferred because of ease of handling. In the case of p-toluenesulfonic acid, the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyhydric hydroxy resin (a).
  • the polyhydric hydroxy resin (a), the catalyst and the solvent are charged into a reactor and dissolved, and then the aromatic vinyl compound is added for 0.1 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.5 to 8 hours. A method of dripping over 5 to 5 hours is good.
  • the reaction temperature is preferably 50-200°C, more preferably 100-180°C, even more preferably 120-160°C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, even more preferably 4 to 8 hours.
  • an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst.
  • solvents such as aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve and washed with water. hydroxy resins can be obtained.
  • Solvents used in the reaction include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethylene glycol dimethyl ether, and diethylene.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • halogenated hydrocarbons such as chlorobenzene and dichlorobenzene
  • ethylene glycol dimethyl ether and diethylene
  • solvents such as ethers such as glycol dimethyl ether. These solvents may be used singly or in combination of two or more.
  • polyhydric hydroxy compound (resin) represented by the above general formula (4) it is preferable to use the polyhydric hydroxy resin obtained by the above reaction, but it is not limited thereto.
  • the allyl etherification method is excellent.
  • a polyhydric hydroxy resin represented by general formula (4) is reacted with an allyl halide compound in a solvent in the presence of an alkali compound (allyl etherification reaction).
  • the polyhydric hydroxy resin is dissolved in advance in a solvent, and then the allyl halide compound and the alkali compound are added and reacted.
  • This allyl etherification reaction is preferably carried out by charging a polyhydric hydroxy resin and a solvent into a reactor, dissolving them, and then adding dropwise an allyl halide compound solution and an alkali compound solution.
  • allyl halide compound used for producing the allyl ether compound examples include allyl chloride, allyl bromide, methallyl chloride, and methallyl bromide.
  • allyl bromide or allyl chloride is preferable from the viewpoint of reactivity with the polyhydric hydroxy resin.
  • allyl chloride tends to polymerize with each other to form a polymer (polyallyl chloride), but it is preferable to use allyl chloride containing a small amount of polyallyl chloride for production.
  • the content of polyallyl chloride in the allyl chloride used is high, not only will the total amount of chlorine in the allyl ether compound to be obtained increase, but it will also contribute to an increase in the molecular weight of the allyl ether compound, resulting in a trace amount in the cured product. There is a risk of generating a gelled product. Moreover, in order to reduce the amount of chlorine, it is necessary to add a considerable amount of a basic substance, which is industrially unfavorable.
  • the content ratio of polyallyl chloride can be easily confirmed by gas chromatography or the like, and the content ratio of polyallyl chloride is preferably 1 area % or less relative to the allyl chloride monomer, and 0.5% by area.
  • the amount of the allyl halide compound used is generally 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, more preferably 1.0 to 1.0 mol, per 1 mol of the hydroxyl group of the polyhydric hydroxy resin. It is 1.25 mol, more preferably 1.0 to 1.2 mol.
  • alkali metal hydroxides, carbonates, and the like are preferable, and specific examples include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. Sodium and potassium hydroxide are preferred.
  • Such an alkali metal hydroxide may be used in a solid state or in a solution state.
  • the amount of the alkali compound to be used is generally 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1.0 mol, per 1 mol of hydroxyl group of the polyhydric hydroxy resin. It is 5 mol, more preferably 1.0 to 1.3 mol, particularly preferably 1.0 to 1.1 mol.
  • the solvent used for the production of the allyl ether compound is not particularly limited, but examples include alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. and ethers such as tetrahydrofuran, dioxane and diglyme, and aprotic polar solvents such as dimethylacetamide, dimethylformamide and dimethylsulfoxide. One or more of these solvents can be used. Moreover, water can also be used by mixing with the above solvent.
  • the amount of solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, particularly preferably 25 to 200% by mass, based on the total mass of the polyhydric hydroxy resin.
  • the aprotic polar solvent is not useful for purification such as washing with water, and has a high boiling point and is difficult to remove. I don't like it.
  • a solvent such as toluene (another organic solvent) may be included. 0.5 to 50% by mass is more preferable.
  • the reaction temperature for the allyl etherification reaction of the polyhydric hydroxy resin is generally 30 to 90°C, preferably 35 to 80°C. In order to obtain an allyl ether compound of higher purity, it is preferable to increase the reaction temperature in two or more stages, for example, 35 to 50° C. in the first stage and 45 to 70° C. in the second stage. is particularly preferred.
  • the reaction time for the allyl etherification reaction of the polyhydric hydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or longer, the reaction proceeds sufficiently, and when the reaction time is 10 hours or shorter, it becomes possible to suppress the amount of by-products produced.
  • the solvent is distilled off under heating under reduced pressure, or without being distilled off, a ketone solvent having 4 to 7 carbon atoms (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), , toluene, etc., and heated to 40 to 90° C., more preferably 50 to 80° C., and washed with water until the pH of the aqueous layer reaches 5 to 8 to remove by-produced salts.
  • a ketone solvent having 4 to 7 carbon atoms eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.
  • the allyl etherification reaction of the polyhydric hydroxy resin is usually carried out while blowing an inert gas such as nitrogen into the system (in the air or in the liquid).
  • an inert gas such as nitrogen
  • the amount of inert gas to be blown per unit time varies depending on the volume of the kettle used for the reaction. is preferably adjusted.
  • the maleimide compound contained in the resin composition of the present invention is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
  • Examples include N-phenylmaleimide and phenylmethane. maleimide, N-hydroxyphenylmaleimide, 4,4′-diphenylmethanebismaleimide, 4,4-diphenyletherbismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2′-[4- (4-maleimidophenoxy)phenyl]propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis- (3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimid
  • R 4 independently represents an alkyl group having 1 to 5 carbon atoms or an aromatic group.
  • R5 independently represents a hydrogen atom or a methyl group.
  • a represents 0 to 4, preferably 0 or 1;
  • b represents 0 to 3, preferably 0 or 1;
  • r and q are 0 or 1;
  • m is the number of repetitions, and its average value is 1 to 10, preferably 1 to 7, more preferably 1 to 5.
  • the resin composition of the present invention contains the allyl ether compound (resin) and maleimide compound (resin) of the present invention as essential components.
  • the content of the allyl ether compound is preferably 5 to 900 parts by mass, more preferably 10 to 500 parts by mass, and still more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the maleimide compound.
  • the allyl ether compound used to obtain the resin composition of the present invention in addition to the allyl ether compound of the present invention, one or more of various allyl ether compounds may be used in combination, if necessary.
  • at least 30% by mass of the allyl ether compound is the allyl ether compound of the present invention, more preferably 50% by mass or more. If it is less than this, the dielectric properties may deteriorate.
  • cresol novolak resins aromatic modified phenol novolak resins, bisphenol A novolak resins, trishydroxyphenylmethane type novolak resins such as Resitop TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), phenols such as naphthol novolak resins, Condensates of naphthols and/or bisphenols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), naphthols and/or bisphenols and xyloxy Condensates with lenglycol, condensates of phenols and/or naphthols with isopropenylacetophenone, reaction products of phenols, naphthols and/or bisphenols with dicyclopentadiene, phenols, naphthols and/or Examples include allyl ether compounds and trially
  • a curing accelerator can be added to the resin composition of the present invention as necessary.
  • a curing accelerator the compound capable of cross-linking reaction with the imide group undergoes an addition reaction with the imide group to cross-link, so that the cured product exhibits good physical properties.
  • curing accelerators include amines, imidazoles, organic phosphines, Lewis acids, organic peroxides, and the like.
  • tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles, tributylphosphine, methyldiphenylphosphine, triphenyl Organic phosphines such as phosphine, diphenylphosphine and phenylphosphine, addition reaction products of organic phosphines and quinone compounds, tetraphenylphosphon
  • the resin composition of the present invention can be blended with other various curable resins and thermoplastic resins.
  • curable resins examples include epoxy resins, unsaturated polyester resins, curable maleimide resins, polycyanate resins, phenolic resins, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. etc. From the viewpoint of low dielectric constant and low dielectric loss tangent, one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule are preferable.
  • the curable resin is an epoxy resin
  • it is preferably one or more epoxy resins selected from epoxy resins having two or more epoxy groups in one molecule.
  • epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, naphthalenediol type epoxy resin, Bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, resorcinol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy resin, ⁇ -naphthol aral
  • a curing agent may be used in addition to the epoxy resin.
  • the curing agent is not particularly limited, and examples thereof include phenol-based curing agents, amine-based compounds, amide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, active ester-based curing agents, and benzoxazine-based curing agents. , cyanate ester curing agents, and the like. These may be used alone, may be used in combination of two or more of the same type, may be used in combination of other types.
  • a curing accelerator when blending an epoxy resin, a curing accelerator can be used as necessary.
  • examples include amines, imidazoles, organic phosphines, and Lewis acids.
  • the amount to be added is usually in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the type is not particularly limited. That is, any vinyl compound may be used as long as it can be cured by forming crosslinks by reacting with the vinyl compound of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, more preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.
  • the average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups); also referred to as the number of terminal double bonds) per molecule of vinyl compounds as curable resins is For example, it is preferably 1 to 20, more preferably 2 to 18, depending on the Mw of the class. If the number of terminal double bonds is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal double bonds is too large, the reactivity becomes too high, and problems such as deterioration of storage stability of the composition and deterioration of fluidity of the composition may occur. be.
  • Vinyl compounds include, for example, triallyl isocyanurate (TAIC) and other trialkenyl isocyanurate compounds, modified polyphenylene ethers (PPE) whose terminals are modified with (meth)acryloyl groups or styryl groups, and (meth) Polyfunctional (meth)acrylate compounds having two or more acryloyl groups, vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds), and vinylbenzyls such as styrene and divinylbenzene compounds and the like.
  • TAIC triallyl isocyanurate
  • PPE modified polyphenylene ethers
  • PPE polyphenylene ethers
  • vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds)
  • vinylbenzyls such as styrene and divinylbenzene compounds and the like.
  • those having two or more carbon-carbon double bonds in the molecule are preferable, and specifically, TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. etc. It is believed that the use of these compounds will result in more favorable formation of crosslinks through the curing reaction, and the heat resistance of the cured product of the resin composition can be further enhanced. Moreover, these may be used independently and may be used in combination of 2 or more type. A compound having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
  • thermoplastic resins include phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, polymethyl methacrylate resins, polycarbonate resins, Polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethersulfone resin, polysulfone resin, polyether ether Ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc., and known thermoplastic elastomers (e.g., styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copo
  • the resin composition of the present invention may contain other additives such as fillers, silane coupling agents, antioxidants, release agents, antifoaming agents, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments, and the like. agents and the like can be contained.
  • fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, carbonate Barium, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer, pigment, etc. be done.
  • One of the reasons for using a filler is the effect of improving the impact resistance. These may be used alone or in combination of two or more.
  • metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide are used, they act as flame retardant aids and have the effect of improving flame retardancy.
  • metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide are used, they act as flame retardant aids and have the effect of improving flame retardancy.
  • silica, mica, and talc are preferred, and spherical silica is more preferred.
  • these 1 type may be used independently and may be used in combination of 2 or more type.
  • the filler may be used as it is, or may be surface-treated with a silane coupling agent such as epoxysilane type or aminosilane type.
  • a silane coupling agent such as epoxysilane type or aminosilane type.
  • vinylsilane type, methacryloxysilane type, acryloxysilane type, and styrylsilane type silane coupling agents are preferable.
  • a silane coupling agent may be added by an integral blend method instead of the method of surface-treating the filler in advance.
  • fibrous fillers are preferred in terms of dimensional stability, bending strength, and the like.
  • a more preferred example is a glass fiber substrate using a fibrous base material filler in which glass fibers are woven into a mesh.
  • the amount of the filler compounded is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 70 parts by mass, based on 100 parts by mass of the resin composition (solid content). If the compounding amount is too large, the cured product becomes brittle, and there is a possibility that sufficient mechanical properties cannot be obtained. On the other hand, if the blending amount is too small, there is a fear that the blending effect of the filler, such as improvement of the impact resistance of the cured product, may not be achieved.
  • the blending amount of other additives is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin composition (solid content).
  • a cured product can be obtained by heat-curing the resin composition of the present invention.
  • Methods for obtaining a cured product include cast molding, compression molding, transfer molding, etc., and methods such as laminating in the form of resin sheets, resin-coated copper foils, prepregs, etc., and curing them under heat and pressure to form laminates. is preferably used.
  • the temperature at this time is usually in the range of 150 to 300° C., and the curing time is usually about 10 minutes to 5 hours.
  • the resin composition of the present invention is obtained by uniformly mixing the above components.
  • the resin composition can be easily cured by a conventionally known method.
  • Examples of cured products include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.
  • the resin composition includes printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor sealing materials, conductive pastes, conductive films, Adhesive films for build-up, resin casting materials, adhesives, and the like.
  • printed wiring board materials, insulating materials for circuit boards, and adhesive film applications for build-up are so-called substrates for embedding electronic components, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate.
  • insulating material can be used as an insulating material for Among these, due to their properties such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility, they can be used as printed wiring board materials, resin compositions for flexible wiring boards, and circuit boards such as interlayer insulation materials for build-up boards ( It is preferably used as a material for laminates) and a semiconductor encapsulating material.
  • Sealing materials obtained using the resin composition of the present invention include tape-shaped semiconductor chips, potting-type liquid sealing, underfill, semiconductor interlayer insulating films, etc., and are preferably used for these. be able to.
  • additives such as inorganic fillers, coupling agents, and mold release agents, which are blended as necessary in the resin composition, are premixed, and then extruded. , a kneader, a roll, or the like, to sufficiently melt and mix until uniform.
  • silica is usually used as the inorganic filler, and it is preferable to blend 70 to 95 mass % of the inorganic filler into the resin composition.
  • the obtained resin composition is cast, or molded using a transfer molding machine, an injection molding machine, etc., and further 180 to 250 C. for 0.5 to 5 hours to obtain a molded product.
  • the obtained resin composition is heated to prepare a semi-cured sheet to form a encapsulating material tape, and then the encapsulating material tape is placed on a semiconductor chip, A method of heating to 100 to 150.degree. C. to soften and mold, and curing completely at 180 to 250.degree.
  • the obtained resin composition may be dissolved in a solvent as necessary, applied onto a semiconductor chip or electronic component, and cured directly.
  • the resin composition of the present invention can be dissolved in an organic solvent to prepare a varnish.
  • Organic solvents that can be used include alcohol solvents such as methanol and ethanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as tetrahydrofuran, and nitrogen solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
  • Atom-containing solvents, sulfur atom-containing solvents such as dimethylsulfoxide, and the like can be mentioned, and one or a mixture of two or more thereof can be used.
  • methyl ethyl ketone and dimethylformamide are preferred in terms of solubility and handling.
  • the resin composition of the present invention is dissolved in an organic solvent to form a composition varnish, impregnated with a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc., and then the solvent is removed to form a prepreg. be able to.
  • a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc.
  • an adhesive sheet can be obtained by applying the composition varnish onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, and the like, followed by drying.
  • a metal foil is arranged on one side or both sides to form a laminate, and the laminate is pressurized and heated.
  • a laminate can be obtained by curing and integrating the prepreg.
  • the metal foil copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil.
  • the conditions for heating and pressurizing the laminate may be appropriately adjusted so that the resin composition is cured. It is desirable to apply pressure under conditions that satisfy moldability.
  • the heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C.
  • the applied pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa.
  • the heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours.
  • a multi-layer board can be produced by using the single-layer laminate board thus obtained as an inner layer material.
  • a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is subjected to a blackening treatment to obtain an inner layer material.
  • An insulating layer is formed on one or both sides of the inner layer material with a prepreg or an adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.
  • hydroxyl equivalent The measurement was performed according to the JIS K0070 standard, and the unit was expressed as "g/eq.”.
  • the hydroxyl group equivalent of the polyhydric hydroxy resin means the phenolic hydroxyl group equivalent.
  • Glass transition temperature (Tg) It was measured according to JIS C6481 standard. It was expressed by tan ⁇ peak top when measured with a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR DMS6100) at a temperature rising condition of 5°C/min.
  • GPC gel permeation chromatography measurement: A column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL manufactured by Tosoh Corporation) in series with a main body (HLC-8220GPC manufactured by Tosoh Corporation) was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as a detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 ⁇ L of the solution was used.
  • THF Tetrahydrofuran
  • Mw and Mn were obtained by conversion from a calibration curve obtained from standard polystyrene (manufactured by Tosoh Corporation, PStQuick Kit-H).
  • GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.
  • IR A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, KRS-5 was used for the cell, and a sample dissolved in THF was applied on the cell and dried. After that, the absorbance at wavenumbers of 450 to 4000 cm ⁇ 1 was measured.
  • ESI-MS Mass spectrometry was performed by using a mass spectrometer (Shimadzu Corporation, LCMS-2020), using acetonitrile and water as mobile phases, and measuring a sample dissolved in acetonitrile.
  • M1 phenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300)
  • M2 maleimide compound obtained in Synthesis Example 5
  • E1 Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 274, softening point 60 ° C.)
  • C1 dicumyl peroxide (manufactured by NOF Co., Ltd., Parkmil D)
  • C2 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curesol 2E4MZ)
  • Synthesis example 1 2,6-xylenol (structural formula below) was added to a reaction apparatus consisting of a glass separable flask equipped with a stirrer, thermometer, nitrogen blowing tube, dropping funnel, and cooling tube. 500 parts and 7.3 parts of 47% BF 3 ether complex were charged and heated to 100° C. while stirring. While maintaining the same temperature, dicyclopentadiene (structural formula below) 67.6 parts (0.12 times mol with respect to 2,6-xylenol) was added dropwise over 1 hour. Further, the mixture was reacted at a temperature of 115 to 125° C. for 4 hours, and 11 parts of calcium hydroxide was added.
  • the resulting polyhydric hydroxy resin (PH1) had a hydroxyl equivalent of 195 and a softening point of 73°C.
  • Synthesis example 2 250 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1, 2.5 parts of p-toluenesulfonic acid monohydrate, and 62.5 parts of MIBK were charged in the same reactor as in Synthesis Example 1 and stirred. It was heated to 120° C. while Divinylbenzene (manufactured by Aldrich, 80% divinylbenzene, 20% ethylvinylbenzene) (structural formula below) was added while maintaining the same temperature. 150 parts (0.90 times mol with respect to PH1) was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene manufactured by Aldrich, 80% divinylbenzene, 20% ethylvinylbenzene
  • R 2 ' is a group represented by formula (5) derived from ethylbenzene (one of R 3 is an ethyl group) and a group represented by formula (6) derived from divinylbenzene (R 3 are all hydrogen atoms) are mixed at almost a blending ratio.
  • Synthesis example 3 In the same reactor as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH1) obtained in Synthesis Example 1, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged and stirred to 120 parts. It was warmed to °C. While maintaining the same temperature, 45 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) (0.67 times mol with respect to pH 1) was added dropwise over 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • R 2 ' is a group represented by formula (5) derived from ethylbenzene (one of R 3 is an ethyl group) and a group represented by formula (6) derived from divinylbenzene (R 3 are all hydrogen atoms) are mixed at almost a blending ratio.
  • Synthesis example 4 In the same reaction apparatus as in Synthesis Example 1, phenol (the following structural formula) 1507 parts and 22.7 parts of 47% BF 3 ether complex were charged and heated to 100° C. while stirring. While maintaining the same temperature, dicyclopentadiene 211.7 parts (0.10 times mol with respect to phenol) was added dropwise over 1 hour. Further, the mixture was reacted at a temperature of 115 to 125° C. for 4 hours, and 36 parts of calcium hydroxide was added. An additional 60 parts of a 10% aqueous oxalic acid solution was added. Then, after heating to 160° C. for dehydration, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials.
  • phenol the following structural formula 1507 parts and 22.7 parts of 47% BF 3 ether complex were charged and heated to 100° C. while stirring. While maintaining the same temperature, dicyclopentadiene 211.7 parts (0.10 times mol with respect to phenol)
  • Synthesis example 5 A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap and a stirrer was charged with 100 parts of aniline and 50 parts of toluene, and 39.2 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the water and toluene that had been azeotroped by heating were cooled and separated, and then only the toluene, which was the organic layer, was returned to the system for dehydration.
  • Example 1 100 parts of the polyhydric hydroxy resin (P1) obtained in Synthesis Example 2 and 150 parts of diglyme were placed in the same reactor as in Synthesis Example 1, heated to 100°C to form a uniform solution, and then heated to about 35°C. cooled to After adding 29 parts of a 50% sodium hydroxide solution (1.1 times the moles of the polyhydric hydroxy resin) to make a phenolate solution, allyl bromide (the following structural formula) was heated in the range of 30 to 40°C. 47 parts (1.2 times mol with respect to the polyhydric hydroxy resin) was added dropwise over 1 hour, and after the dropwise addition was completed, the temperature was raised to 60° C. and the reaction was carried out at the same temperature for 3 hours.
  • a 50% sodium hydroxide solution 1.1 times the moles of the polyhydric hydroxy resin
  • allyl bromide the following structural formula
  • the reaction mixture was heated to 130° C. under a reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 109 parts of brown allyl ether compound (R1).
  • the obtained allyl ether compound (R1) had a softening point of 51° C., a hydroxyl equivalent of 12180, a melt viscosity at 150° C. of 0.15 Pa ⁇ s, and a total chlorine content of 77 ppm.
  • R 2 is a group represented by formula (5) derived from ethylbenzene (one of R 3 is an ethyl group) and a group represented by formula (6) derived from divinylbenzene (R 3 is all hydrogen atoms) are mixed at almost a blending ratio.
  • R9 is a hydrogen atom.
  • Example 2 100 parts of the polyhydric hydroxy resin (P2) obtained in Synthesis Example 3 and 150 parts of diglyme were placed in the same reactor as in Synthesis Example 1, heated to 100°C to form a uniform solution, and then heated to about 35°C. cooled to After adding 33 parts of 50% sodium hydroxide solution (1.1 times mol with respect to the polyhydroxy resin) to make a phenolate solution, 53 parts of allyl bromide (with respect to the polyhydroxy resin) was added in the range of 30 to 40 ° C. 1.2 times mol) was added dropwise over 1 hour, and after the completion of the dropwise addition, the temperature was raised to 60° C., and the reaction was carried out at the same temperature for 3 hours.
  • R 2 is a group represented by formula (5) derived from ethylbenzene (one of R 3 is an ethyl group) and a group represented by formula (6) derived from divinylbenzene (R 3 is all hydrogen atoms) are mixed at almost a blending ratio.
  • R9 is a hydrogen atom.
  • Reference example 1 An allyl ether compound (S1) was obtained in the same manner as in Example 1, except that the polyhydric hydroxy resin was changed to P3.
  • Reference example 2 An allyl ether compound (S2) was obtained in the same manner as in Example 1, except that the polyhydric hydroxy resin was changed to MEH.
  • Example 3 100.0 parts of the maleimide compound (M1), 188.4 parts of the allyl ether compound (R1) obtained in Example 1, and 2.9 parts of the curing accelerator (C1) were blended and dissolved in methyl ethyl ketone (MEK). As a result, a resin composition varnish having a resin concentration of 50% was obtained.
  • a glass cloth (WEA 7628 XS13, manufactured by Nitto Boseki Co., Ltd., 0.18 mm thick) was impregnated with the obtained resin composition varnish. The impregnated glass cloth was dried in a hot air circulating oven at 150° C. for 10 minutes to obtain a prepreg.
  • the obtained prepreg was loosened and passed through a sieve to obtain powdery prepreg powder of 100 mesh.
  • the obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under temperature conditions of 130° C. ⁇ 15 minutes+220° C. ⁇ 120 minutes to obtain a cured resin test piece of 50 mm square ⁇ 2 mm thickness.
  • Table 1 shows the measurement results of the dielectric constant and dielectric loss tangent of the test piece.
  • Examples 4-6, Comparative Examples 1-4 A resin composition varnish was obtained by blending in the amount (parts) of the formulation shown in Table 1, using the same equipment as in Example 3, and performing the same operation, and further obtaining a laminate and a cured resin test piece. . The same test as in Example 3 was conducted, and the results are shown in Table 1.
  • the allyl ether compound (resin) of the present invention is particularly useful for laminates and electronic circuit boards that require low dielectric constant and low dielectric loss tangent.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
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Abstract

L'invention concerne : un composé éther d'allyle qui permet d'obtenir un produit durci qui est excellent du fait qu'il présente de faibles propriétés diélectriques, une forte résistance à la chaleur, et analogues ; une composition de résine associée ; et un produit durci obtenu à partir de ladite composition de résine.　Le composé éther d'allyle est représenté par la formule générale (1).　
PCT/JP2022/024563 2021-06-30 2022-06-20 Composé éther d'allyle, composition de résine associée, produit durci associé et procédé de production d'un composé éther d'allyle Ceased WO2023276760A1 (fr)

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CN119638893A (zh) * 2024-12-26 2025-03-18 东北师范大学 一种具有自修复功能的极性3,4-异戊胶及其制备方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
US4540829A (en) * 1982-12-02 1985-09-10 The Dow Chemical Company Allylated di or polycyclopentadiene diphenols
JPH08127706A (ja) * 1994-10-31 1996-05-21 Dainippon Ink & Chem Inc 硬化性樹脂組成物、プリプレグ、コンパウンド及び硬化物
JP2002194215A (ja) * 2000-12-26 2002-07-10 Kanegafuchi Chem Ind Co Ltd 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2015000970A (ja) * 2013-06-18 2015-01-05 第一工業製薬株式会社 非水性分散媒用分散剤
WO2016076115A1 (fr) * 2014-11-11 2016-05-19 第一工業製薬株式会社 Composition d'adhésif, et adhésif
JP6852209B1 (ja) * 2020-06-02 2021-03-31 第一工業製薬株式会社 水分散体、金属用コーティング剤および塗膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4540829A (en) * 1982-12-02 1985-09-10 The Dow Chemical Company Allylated di or polycyclopentadiene diphenols
JPH08127706A (ja) * 1994-10-31 1996-05-21 Dainippon Ink & Chem Inc 硬化性樹脂組成物、プリプレグ、コンパウンド及び硬化物
JP2002194215A (ja) * 2000-12-26 2002-07-10 Kanegafuchi Chem Ind Co Ltd 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
JP2015000970A (ja) * 2013-06-18 2015-01-05 第一工業製薬株式会社 非水性分散媒用分散剤
WO2016076115A1 (fr) * 2014-11-11 2016-05-19 第一工業製薬株式会社 Composition d'adhésif, et adhésif
JP6852209B1 (ja) * 2020-06-02 2021-03-31 第一工業製薬株式会社 水分散体、金属用コーティング剤および塗膜

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119638893A (zh) * 2024-12-26 2025-03-18 东北师范大学 一种具有自修复功能的极性3,4-异戊胶及其制备方法

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