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WO2018199156A1 - Résine contenant un groupe méthallyle, composition de résine durcissable et produit durci de cette dernière - Google Patents

Résine contenant un groupe méthallyle, composition de résine durcissable et produit durci de cette dernière Download PDF

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Publication number
WO2018199156A1
WO2018199156A1 PCT/JP2018/016783 JP2018016783W WO2018199156A1 WO 2018199156 A1 WO2018199156 A1 WO 2018199156A1 JP 2018016783 W JP2018016783 W JP 2018016783W WO 2018199156 A1 WO2018199156 A1 WO 2018199156A1
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Prior art keywords
group
methallyl
resin composition
curable resin
weight
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PCT/JP2018/016783
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English (en)
Japanese (ja)
Inventor
窪木　健一
一貴 松浦
政隆 中西
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日本化薬株式会社
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Priority to JP2019514570A priority Critical patent/JP6979746B2/ja
Publication of WO2018199156A1 publication Critical patent/WO2018199156A1/fr

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    • 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
    • C08F12/00—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 aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals

Definitions

  • the present invention relates to a methallyl group-containing resin, a curable resin composition, and a cured product thereof, and includes a semiconductor element sealing material, a liquid crystal display element sealing material, and an electroluminescent element (hereinafter referred to as “EL”).
  • EL electroluminescent element
  • Suitable for electrical and electronic parts such as sealing materials for printed circuit boards, printed wiring boards, build-up laminates, lightweight high-strength materials such as carbon fiber reinforced composite materials (hereinafter referred to as “CFRP”) and glass fiber reinforced composite materials used.
  • Patent Documents 3 and 4 disclose a resin composition of a maleimide resin and a propenyl group-containing phenol resin.
  • Patent Document 2 discloses a resin composition of a maleimide resin and an allyl group-containing phenol resin.
  • Patent Document 1 uses a phenol resin substituted with a propenyl group, the dielectric properties are insufficient. Further, in Patent Document 2, all phenolic resins substituted with allyl groups are used, so the reactivity is poor and the dielectric properties are still not sufficient, and further improvements are required. Therefore, the present invention provides a methallyl group-containing resin, a curable resin composition, and a cured product thereof that exhibit excellent low hygroscopicity (low water absorption), dielectric properties, and heat resistance in the cured product.
  • multiple Zs each independently represent a single bond, a hydrocarbon group having 6 to 18 carbon atoms including an aromatic ring, a carbon atom to which a heterocyclic ring is bonded, an isobenzofuran group analog, or an isoindole group analog.
  • multiple Ys each independently represent a hydrogen atom or a methallyl group, and 20% or more of the total number of Y is a methallyl group.
  • n is an average value and represents a real number of 1 to 20.
  • m is an average value and represents a real number of 0 to 10, provided that m is 0 Z is not a single bond or a fluorene group, and a dotted line indicates that a phenyl group may be present.
  • the cured product of the resin composition using the methallyl group-containing resin of the present invention exhibits excellent low moisture absorption (low water absorption), heat resistance (solder reflow resistance), and dielectric properties. Therefore, insulating materials for electrical and electronic parts (such as highly reliable semiconductor sealing materials) and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), liquid crystal sealing materials, EL sealing materials, adhesives (conductive) Adhesives, etc.), various composite materials including CFRP, and paints.
  • the methallyl group-containing resin of the present invention is represented by the following formula (1).
  • multiple Zs each independently represent a single bond, a hydrocarbon group having 6 to 18 carbon atoms including an aromatic ring, a carbon atom to which a heterocyclic ring is bonded, an isobenzofuran group analog, or an isoindole group analog.
  • multiple Ys each independently represent a hydrogen atom or a methallyl group, and 20% or more of the total number of Y is a methallyl group.
  • n is an average value and represents a real number of 1 to 20.
  • m is an average value and represents a real number of 0 to 10, provided that m is 0 Z is not a single bond or a fluorene group, and a dotted line indicates that a phenyl group may be present.
  • the methallyl group-containing resin of the present invention When mixed with a reactive olefin resin containing a maleimide group or an acrylate group, the methallyl group-containing resin of the present invention has a lower hygroscopicity than the allyl group-containing resin or propenyl group-containing resin of the same skeleton, and has dielectric properties. A good cured product can be obtained.
  • polar groups are not generated, so that it is possible to suppress an increase in water absorption (humidity) due to improved heat resistance.
  • a plurality of Z are each independently a single bond, a hydrocarbon group having 6 to 18 carbon atoms including an aromatic ring, a carbon atom to which a heterocyclic ring is bonded, an isobenzofuran group analog, an isoindole group Represents an analog.
  • the hydrocarbon group containing an aromatic ring preferably has 6 to 12 carbon atoms.
  • a thiophene ring, a furan ring, and a pyridine ring are more preferable.
  • the isobenzofuran group analog means a structure represented by the following formula (A), wherein R 1 is preferably a hydrogen atom.
  • the isoindole group analog means a structure represented by the following formula (B), in which R 2 is preferably a hydrogen atom or an aromatic group, more preferably an aromatic group.
  • R 2 is preferably a hydrogen atom or an aromatic group, more preferably an aromatic group.
  • a plurality of Y each independently represents a hydrogen atom or a methallyl group, and 20% or more of the total number of Y is a methallyl group, more preferably 30% or more, particularly Preferably it is 40% or more.
  • 20% or more of the total number of Y is a methallyl group, the heat resistance is improved.
  • it is not the definition of one molecular unit of the corresponding compound, but means the average of a plurality of molecules of the corresponding compound.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group.
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group.
  • P represents 1 to 4). (* Represents a bonding position.)
  • Z in the formula (1) include the following structures, but are not limited thereto. Note that * represents a bonding position.
  • the structure is as follows in Z exemplified above.
  • the average value of n is a real number of 1 to 20, preferably 1 to 10, and particularly preferably 1 to 6.
  • the manufacturing method of the methallyl group containing resin of this invention is demonstrated.
  • the methallyl group-containing resin of the present invention described in the above (1) is obtained by using a phenol resin of the following formula (2) as a raw material, synthesizing a methallyl ether, and rearranging the methallyl group by Claisen rearrangement.
  • multiple Zs each independently represent a single bond, a hydrocarbon group having 6 to 18 carbon atoms including an aromatic ring, a carbon atom to which a heterocyclic ring is bonded, an isobenzofuran group analog, or an isoindole group analog.
  • a plurality of R's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a methoxy group or an ethoxy group, n is an average value and represents a real number of 1 to 20, m is an average value And represents a real number of 0 to 10.
  • n is an average value and represents a real number of 1 to 20
  • m is an average value
  • Z is not a single bond or a fluorene group, and a dotted line indicates that a phenyl group may be present.
  • the reaction for converting the hydroxyl group of the phenol resin represented by the formula (2) to methallyl ether is a known method, and generally methallyl chloride, methallyl bromide, methallyl iodide using a base such as an alkali metal hydroxide. A methallyl ether such as methallyl halide is reacted.
  • a highly polar solvent such as methanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone is used. It is preferable to use it.
  • the amount of the polar solvent used is usually 50 to 400 parts by weight, preferably 70 to 300 parts by weight, based on 100 parts by weight of the raw material. These may be used alone or in combination, and a solvent having low polarity such as toluene or xylene may be used in combination.
  • the amount of methallyl halide and base used is usually 0.1 to 2.0 mol, preferably 0.2 to 1.5 mol, based on 1 equivalent of the hydroxyl group of the phenol resin.
  • the rate can be adjusted.
  • a phenol resin is dissolved in the above-mentioned isopropanol or dimethyl sulfoxide, and then an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. After dissolving the alkali metal hydroxide at 50 to 100 ° C., 30 to 50 Add methallyl chloride or methallyl bromide at 2 ° C. over 2 to 5 hours, and then react at 30 to 70 ° C. for 1 to 10 hours.
  • the Claisen rearrangement reaction of the obtained methallyl ether may be carried out according to a conventional method.
  • a compound having a methallyl ether group may be used in the presence of a high-boiling solvent such as carbitol, paraffin oil, N, N′-dimethylaniline, or solvent-free. Under heating at 150-230 ° C. for 0.5-100 hours.
  • the solvent is used as required in an amount of 10 to 200 parts by weight based on 100 parts by weight of methallyl ether. After completion of the reaction, the solvent used can be removed if necessary to obtain a methallylated phenol resin.
  • the reaction is preferably performed in a vacuum or in an inert gas atmosphere such as nitrogen or argon, and the product can be prevented from being colored.
  • an antioxidant may be added to perform the Claisen rearrangement.
  • the antioxidant is preferably used in an amount of about 10 parts by weight per 100 parts by weight of methallyl ether.
  • Phenol antioxidants include methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, tert-butylated bisphenol A, 2,2'-methylenebis (4-methyl- 6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-ethylidenebis (3-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) buta 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl
  • the curable resin composition of the present invention contains the methallyl group-containing resin of the present invention and can contain a compound having a functional group that reacts by heating.
  • the curable resin composition of the present invention may contain a maleimide compound.
  • a conventionally well-known maleimide compound can be used as a maleimide compound which can be mix
  • Specific examples of the maleimide compound include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3 '-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like, but are not limited thereto.
  • the blending amount of the maleimide compound is preferably not more than 5 times, more preferably not more than 2 times the weight of the methallyl group-containing resin of the present invention.
  • maleimide compounds described in Japanese Patent Application Laid-Open No. 2009-001783 (Patent Document 3) and Japanese Patent Application Laid-Open No. 01-294661 (Patent Document 4) have low hygroscopicity, flame retardancy, and dielectric properties. Since it is excellent in characteristics, it is particularly preferable as a maleimide compound.
  • a radical polymerization initiator for reacting methallyl groups of the methallyl group-containing resin of the present invention with each other or a methallyl group and a maleimide group.
  • the radical polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctate, and t-butyl peroxy.
  • Organic peroxides such as benzoate and lauroyl peroxide, azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile), etc.
  • the well-known hardening accelerator of an azo type compound is mentioned, It does not specifically limit to these.
  • the amount is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the curable resin composition.
  • the curable resin composition of the present invention may contain an epoxy resin.
  • an epoxy resin that can be blended in the curable resin composition of the present invention any conventionally known epoxy resin can be used.
  • Specific examples of epoxy resins include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensation of bisphenols and various aldehydes.
  • examples include, but are not limited to, epoxy resins, glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins. These may be used alone or in combination of two or more.
  • a phenol aralkyl resin obtained by condensation reaction of phenols and the above-mentioned bishalogenomethyl aralkyl derivative or aralkyl alcohol derivative, and an epoxy resin obtained by dehydrochlorination reaction with epichlorohydrin are low hygroscopic, Since it is excellent in a flame retardance and a dielectric characteristic, it is especially preferable as an epoxy resin.
  • an epoxy resin curing catalyst (curing accelerator) can be blended as necessary.
  • imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine
  • Amines such as triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine, Examples thereof include phosphines such as tributylphosphine and trioctylphosphine.
  • the amount of the curing catalyst is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based
  • the curable resin composition of the present invention contains the above-described epoxy resin, in a preferred embodiment thereof, it contains various epoxy resin curing agents.
  • the epoxy resin curing agent amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like can be used.
  • Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride.
  • the amount of the epoxy resin curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents per 1 equivalent of epoxy group (or glycidyl group). When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
  • the curable resin composition of the present invention may contain a cyanate ester resin.
  • a conventionally well-known cyanate ester compound can be used as a cyanate ester compound which can be mix
  • Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensates of bisphenols and various aldehydes. Examples include, but are not limited to, cyanate ester compounds obtained by reacting a condensate with cyanogen halide. These may be used alone or in combination of two or more.
  • phenols examples include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.
  • aldehydes examples include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde.
  • Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene.
  • Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
  • cyanate ester resin examples include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl).
  • the curable resin composition of the present invention contains a cyanate ester resin, zinc naphthenate, cobalt naphthenate, copper naphthenate are used to form a sym-triazine ring by trimerizing cyanate groups as necessary.
  • Catalysts such as lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, and dibutyltin maleate can also be included.
  • the catalyst is usually used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the curable resin composition.
  • the curable resin composition of the present invention includes fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride as necessary.
  • Powders such as forsterite, steatite, spinel, mullite, titania, talc, etc., or various fillers such as inorganic fillers, silane coupling agents, mold release agents, pigments, etc., in which these are spherical or crushed
  • a thermosetting resin or the like can be added.
  • the amount of the inorganic filler used is usually 80 to 92% by weight, preferably 83 to 90% by weight in the curable resin composition. is there.
  • the curable resin composition of the present invention can contain known additives as required.
  • additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and silica, alumina, quartz powder, Aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder and other inorganic fillers, filler surface treatments such as silane coupling agents, mold release agents, carbon black And colorants such as phthalocyanine blue and phthalocyanine green.
  • the amount of these additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, with respect to 100 parts by weight of the curable resin composition.
  • the method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed evenly or prepolymerized.
  • the methallyl group-containing resin and the maleimide compound are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent.
  • a methallyl group-containing resin and a maleimide resin, and if necessary, an epoxy resin, an amine compound, a cyanate ester resin, a phenol resin, an acid anhydride compound, and other additives may be added for prepolymerization.
  • an extruder 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 stirrer is used in the presence of a solvent.
  • the curable resin composition of the present invention is obtained by uniformly mixing each of the above components at a predetermined ratio, and is usually precured at 130 to 180 ° C. for 30 to 500 seconds, and further 150 to 200 ° C. And after curing for 2 to 15 hours, a sufficient curing reaction proceeds and the cured product of the present invention is obtained.
  • the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed and then cured.
  • the cured product of the present invention thus obtained has low hygroscopicity, high heat resistance, and dielectric properties. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring low hygroscopicity, high heat resistance, and dielectric properties. Specifically, it is useful as a material for all electrical and electronic components such as an insulating material, a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, and a resist. In addition to molding materials and composite materials, they can also be used in fields such as paint materials and adhesives. In particular, in soldering for semiconductor elements, solder reflow resistance is beneficial.
  • the curable resin composition of the present invention can be applied to a semiconductor device using the cured product for sealing.
  • semiconductor devices for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package).
  • An organic solvent can be added to the curable resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as “varnish”).
  • the organic solvent used include amide solvents such as ⁇ -butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, tetramethylene sulfone, etc.
  • Sulfones diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether and other ether solvents, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and other ketones And aromatic solvents such as toluene and xylene.
  • the solvent is used in the range where the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.
  • a prepreg can be obtained by heating and melting the curable resin composition of the present invention to lower the viscosity and impregnating the fiber with a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber. Moreover, a prepreg can also be obtained by impregnating the varnish into a reinforcing fiber and drying by heating. The above prepreg is cut into a desired shape, laminated with copper foil as necessary, and then the curable resin composition is heated and cured while applying pressure to the laminate by a press molding method, autoclave molding method, sheet winding molding method, etc. Thus, a laminated board for electric and electronic (printed wiring board) and a carbon fiber reinforced composite material can be obtained.
  • a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber.
  • a prepreg can also be obtained by impregnating the varnish into a reinforcing fiber and drying by heating.
  • the above prepreg is cut into
  • melt viscosity and softening point were measured under the following conditions.
  • Melt viscosity Melt viscosity in the cone plate method.
  • Softening point Measured by a method according to JIS K-7234.
  • the ratio of the methallyl group to the total number of Y in the formula (1) was confirmed by 1 H-NMR (JNM-EC400, manufactured by JEOL Ltd.).
  • Example 1 A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, 25 parts by weight of water, 600 parts by weight of dimethyl sulfoxide, and a phenol resin represented by the following formula (3) (hereinafter referred to as “BPN”). 525 parts by weight of a softening point of 74 ° C., a melt viscosity of 0.16 Pa ⁇ s, and a hydroxyl group equivalent of 210 g / eq) were added, and the mixture was heated to 45 ° C. and dissolved.
  • BPN phenol resin represented by the following formula (3)
  • the mixture was cooled to 38 to 40 ° C., and 110.0 parts by weight of flake caustic soda (purity: 99%, manufactured by Tosoh Corp.) (1.1 molar equivalents relative to 1 molar equivalent of hydroxyl group of BPN) was added over 60 minutes. Thereafter, 250 parts by weight of methallyl chloride (purity: 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.1 molar equivalents relative to 1 molar equivalent of hydroxyl group of BPN) was further added dropwise over 60 minutes and left at 38-40 ° C. for 5 hours. The reaction was performed at 60 to 65 ° C. for 1 hour.
  • BPN-ME BPN methallyl ether
  • BMPN methallylated BPN
  • the softening point of the obtained BMPN was 50.4 ° C.
  • the melt viscosity at 150 ° C. was 0.125 Pa ⁇ s
  • the methallyl group was 96% with respect to the total number of Y in the formula (1).
  • n is an average value and represents a number from 1 to 10.
  • Example 2 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by weight of dimethyl sulfoxide and a phenol resin represented by the following formula (4) (hereinafter referred to as “PXLC”. Hydroxyl equivalent 170 g / eq. Softening point 65 C. 510 parts by weight of MEH (C) -7800-SS manufactured by Meiwa Kasei Co., Ltd., 272 parts by weight of methallyl chloride (purity 99% manufactured by Tokyo Chemical Industry) (1.1 moles relative to 1 mole equivalent of hydroxyl group of phenol resin) Equivalent) and heated to 27 ° C. to dissolve.
  • PXLC Hydroxyl equivalent 170 g / eq.
  • MEH (C) -7800-SS manufactured by Meiwa Kasei Co., Ltd.
  • methallyl chloride purity 99% manufactured by Tokyo Chemical Industry
  • PXLC-ME PXLC methallyl ether resin
  • MPXLC methallylated PXLC
  • the softening point of the obtained MPXLC was 64 ° C.
  • the melt viscosity at 150 ° C. was 0.218 Pa ⁇ s
  • the methallyl group was 95% with respect to the total number of Y in the formula (1).
  • n is an average value and represents a number from 1 to 10.
  • Example 3 A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while 700 parts by weight of dimethyl sulfoxide, a trisphenol methane type phenol resin represented by the following formula (5) (hereinafter referred to as “TPM”).
  • TPM trisphenol methane type phenol resin
  • caustic soda purity: 99%, manufactured by Tosoh Corp.
  • the reaction was carried out at 30 to 35 ° C. for 4 hours, at 40 to 45 ° C. for 1 hour, and at 60 to 65 ° C. for 1 hour.
  • water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure.
  • 600 parts by weight of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral.
  • 523 parts by weight of methallyl ether resin (hereinafter referred to as “TPM-ME”) was obtained by distilling off the solvents from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure.
  • TMPM methallylated TPM
  • n is an average value and represents a number from 1 to 10.
  • Example 4 A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 900 parts by weight of dimethyl sulfoxide, ⁇ , ⁇ -bis (4-hydroxyphenyl) -4- represented by the following formula (6) 494 parts by weight of (4-hydroxy- ⁇ , ⁇ -dimethylbenzyl) -ethylbenzene (hereinafter referred to as “TPPA”, TrisP-PA manufactured by Honshu Chemical Industry), 349 parts by weight of methallyl chloride (purity 99% manufactured by Tokyo Chemical Industry Co., Ltd.) (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added, and the mixture was heated to 27 ° C.
  • TPPA (4-hydroxy- ⁇ , ⁇ -dimethylbenzyl) -ethylbenzene
  • TPPA-ME methallyl ether resin
  • TMPPA methallylated TPPA
  • Example 5 While purging a flask equipped with a stirrer, a reflux condenser, and a stirrer with nitrogen purge, 900 parts by weight of dimethyl sulfoxide and 492 weights of a phenol compound represented by the following formula (7) (hereinafter referred to as “PPPBP”). Part, 249 parts by weight of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was heated to 27 ° C. and dissolved.
  • PPPBP a phenol compound represented by the following formula (7)
  • caustic soda purity: 99%, manufactured by Tosoh Corp.
  • 70 parts by weight of water were added over 60 minutes.
  • the reaction was carried out at 30 to 35 ° C. for 4 hours, at 40 to 45 ° C. for 1 hour, and at 60 to 65 ° C. for 1 hour.
  • water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure.
  • 1500 parts by weight of methyl isobutyl ketone was added and cooled to precipitate crystals.
  • PPPBP-ME methallyl ether compound
  • 200 parts by weight of the obtained PPPBP-ME was charged into a reaction vessel, the degree of vacuum in the system was set to ⁇ 730 mmHg, heated with stirring, reacted at 200 ° C. for 5 hours, and subjected to Claisen rearrangement to produce methallylated PPPBP (hereinafter referred to as “PPBP-ME”).
  • PPBP-ME methallylated PPPBP
  • PPPBMP methallylated PPPBP
  • Example 1 Comparative Synthesis Example 1 In Example 1, the same operation was performed except that 250 parts by weight of methallyl chloride was changed to 211 parts by weight of allyl chloride to obtain allylated BPN (hereinafter referred to as “BAPN”).
  • BAPN allylated BPN
  • Example 2 Comparative Synthesis Example 2 In Example 2, the same operation was performed except that 272 parts by weight of methallyl chloride was changed to 230 parts by weight of allyl chloride to obtain allylated PXLC (hereinafter referred to as “APXLC”).
  • APXLC allylated PXLC
  • Example 3 Comparative Synthesis Example 3 In Example 3, the same operation was performed except that 349 parts by weight of methallyl chloride was changed to 295 parts by weight of allyl chloride to obtain an allylated TPM (hereinafter referred to as “TAPM”).
  • TAPM allylated TPM
  • Example 4 Comparative Synthesis Example 4 In Example 4, the same operation was carried out except that 349 parts by weight of methallyl chloride was changed to 295 parts by weight of allyl chloride to obtain allylated TPPA (hereinafter referred to as “TAPPA”).
  • TAPPA allylated TPPA
  • Example 5 Comparative Synthesis Example 5 In Example 5, the same operation was performed except that 249 parts by weight of methallyl chloride was changed to 210 parts by weight of allyl chloride to obtain allylated PPPBP (hereinafter referred to as “PPPBAP”).
  • PPPBAP allylated PPPBP
  • Examples 6 to 10, Comparative Examples 6 to 10 The methallyl group-containing resin, allyl group-containing resin, and maleimide (MIR-3000 manufactured by Nippon Kayaku Co., Ltd.) obtained in Examples and Comparative Synthesis Examples were blended in the proportions (parts by weight) shown in Table 1, and after heating and melt mixing, It was cast and cured at 200 ° C. for 1 hour and 230 ° C. for 1 hour. The results of measuring the physical properties of the cured product thus obtained for the following items are shown in Table 1.
  • Hygroscopic evaluation Glass transition temperature: Temperature measured by a dynamic viscoelasticity tester and tan ⁇ is a maximum value.
  • Hygroscopic evaluation Hygroscopicity: Weight increase rate after 24 hours at 121 ° C./100%.
  • the test piece is a disk having a diameter of 50 mm and a thickness of 4 mm.
  • Dielectric constant and dielectric loss tangent (Measured at 1 GHz in accordance with K6991 (Cavity Resonator, Agilent Technologies).
  • the cured product of the composition using the methallyl group-containing resin of the present invention has excellent heat resistance (solder reflow resistance) and excellent low hygroscopicity (low) compared to the allyl group-containing resin of the comparative example. It can be confirmed that water absorption and dielectric properties are exhibited.
  • the methallyl group-containing resin of the present invention includes an insulating material for electrical and electronic parts (high reliability semiconductor encapsulating material, etc.), a laminated board (printed wiring board, a substrate for BGA, a buildup board, etc.), an adhesive (conductive adhesive). Etc.), for various composite materials such as CFRP, and paints.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne : une résine contenant un groupe méthallyle qui permet à une composition de résine durcissable de fournir un produit durci présentant un pouvoir absorbant excellemment faible pour l'humidité, une excellente résistance à la chaleur et d'excellentes caractéristiques diélectriques, si elle est utilisée dans la composition de résine durcissable ; une composition de résine durcissable ; et un produit durci de la composition de résine durcissable. Une résine contenant un groupe méthallyle selon la présente invention est représentée par la formule (1). (Dans la formule, Z représente une liaison simple, un groupe hydrocarboné, un atome de carbone auquel est lié un noyau hétérocyclique, ou analogue ; chaque Y représente un atome d'hydrogène ou un groupe méthallyle, et au moins 20 % de toutes les fractions Y sont des groupes méthallyle ; chaque R représente un atome d'hydrogène ou analogue ; n représente une moyenne qui est un nombre réel de 1 à 20 ; m représente une moyenne qui est un nombre réel de 0 à 10, à condition que, dans les cas où m vaut 0, Z n'est pas une liaison simple ni un groupe fluorène ; et la ligne en pointillé indique la présence éventuelle d'un groupe phényle).
PCT/JP2018/016783 2017-04-27 2018-04-25 Résine contenant un groupe méthallyle, composition de résine durcissable et produit durci de cette dernière WO2018199156A1 (fr)

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JPH05230368A (ja) * 1992-02-19 1993-09-07 Toagosei Chem Ind Co Ltd 熱硬化性樹脂組成物
JPH05239155A (ja) * 1992-02-28 1993-09-17 Toagosei Chem Ind Co Ltd 低粘度熱硬化性樹脂組成物
JPH07268068A (ja) * 1994-04-04 1995-10-17 Toagosei Co Ltd 耐熱性樹脂硬化物の製造方法
JPH07268078A (ja) * 1994-03-31 1995-10-17 Toagosei Co Ltd 耐熱性樹脂硬化物の製造方法
JPH07268074A (ja) * 1994-03-31 1995-10-17 Toagosei Co Ltd 熱硬化性樹脂組成物
JPH07330831A (ja) * 1994-06-14 1995-12-19 Toagosei Co Ltd 樹脂組成物
JPH09188666A (ja) * 1995-11-23 1997-07-22 Ciba Geigy Ag ビス（レソルシニル）トリアジン
JP2002356668A (ja) * 2001-05-30 2002-12-13 Fuji Photo Film Co Ltd 紫外線吸収剤及びその製造方法、紫外線吸収剤を含有する組成物、ならびに画像形成方法
JP2014040358A (ja) * 2012-08-24 2014-03-06 Nippon Paper Industries Co Ltd セメント混和剤およびこれを用いたセメント組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05186382A (ja) * 1992-01-08 1993-07-27 Toagosei Chem Ind Co Ltd メタリルフェノール化合物
JPH05230368A (ja) * 1992-02-19 1993-09-07 Toagosei Chem Ind Co Ltd 熱硬化性樹脂組成物
JPH05239155A (ja) * 1992-02-28 1993-09-17 Toagosei Chem Ind Co Ltd 低粘度熱硬化性樹脂組成物
JPH07268078A (ja) * 1994-03-31 1995-10-17 Toagosei Co Ltd 耐熱性樹脂硬化物の製造方法
JPH07268074A (ja) * 1994-03-31 1995-10-17 Toagosei Co Ltd 熱硬化性樹脂組成物
JPH07268068A (ja) * 1994-04-04 1995-10-17 Toagosei Co Ltd 耐熱性樹脂硬化物の製造方法
JPH07330831A (ja) * 1994-06-14 1995-12-19 Toagosei Co Ltd 樹脂組成物
JPH09188666A (ja) * 1995-11-23 1997-07-22 Ciba Geigy Ag ビス（レソルシニル）トリアジン
JP2002356668A (ja) * 2001-05-30 2002-12-13 Fuji Photo Film Co Ltd 紫外線吸収剤及びその製造方法、紫外線吸収剤を含有する組成物、ならびに画像形成方法
JP2014040358A (ja) * 2012-08-24 2014-03-06 Nippon Paper Industries Co Ltd セメント混和剤およびこれを用いたセメント組成物

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