WO2019078300A1 - Composition de résine durcissable, vernis, préimprégné, produit durci, stratifié et stratifié recouvert de cuivre - Google Patents

Composition de résine durcissable, vernis, préimprégné, produit durci, stratifié et stratifié recouvert de cuivre Download PDF

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WO2019078300A1
WO2019078300A1 PCT/JP2018/038852 JP2018038852W WO2019078300A1 WO 2019078300 A1 WO2019078300 A1 WO 2019078300A1 JP 2018038852 W JP2018038852 W JP 2018038852W WO 2019078300 A1 WO2019078300 A1 WO 2019078300A1
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resin
resin composition
curable resin
group
mass
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PCT/JP2018/038852
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English (en)
Japanese (ja)
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一貴 松浦
政隆 中西
窪木　健一
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日本化薬株式会社
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Priority to CN201880064594.9A priority Critical patent/CN111164127A/zh
Priority to JP2019512853A priority patent/JP6515255B1/ja
Publication of WO2019078300A1 publication Critical patent/WO2019078300A1/fr

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    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20

Definitions

  • the present invention relates to a curable resin composition containing a maleimide resin and a benzoxazine resin, a varnish, a prepreg, a cured product, and a laminate or a copper-clad laminate.
  • maleimide resin and benzo useful in insulating materials for electric and electronic parts, semiconductor sealing material applications, laminates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, etc.
  • the present invention relates to a curable resin composition containing an oxazine resin and a cured product thereof.
  • epoxy resins which are thermosetting resins
  • epoxy resins By curing with a variety of curing agents, epoxy resins, which are thermosetting resins, generally become cured products excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as paints, laminates, molding materials, casting materials, and sealing materials. In recent years, with the expansion of the field of use of laminates on which electrical and electronic components are mounted, the required characteristics have been broadened and advanced.
  • Patent Document 2 describes that a mixture of a benzoxazine resin having a bisphenol F skeleton and a maleimide resin is used to improve heat resistance.
  • desmear treatment for removing such resin smear is essential. Desmear treatment is performed, for example, using a permanganate such as potassium permanganate.
  • Patent Document 2 the technology described in Patent Document 2 is not sufficient to obtain the characteristics of the dielectric loss tangent.
  • the amount of resin smear removed by desmear treatment (desmear etching amount) is large, deformation of a hole, peeling of copper foil and the like occur, which causes a decrease in conduction reliability, so to reduce the amount of desmear etching
  • chemical resistance (acid resistance, alkali resistance and desmear liquid resistance) is required.
  • the present invention has been made in view of such a situation, and is excellent in solvent solubility, and a cured product thereof is a maleimide resin excellent in heat resistance, thermal decomposition characteristics, water absorption characteristics, dielectric characteristics, and chemical resistance.
  • An object of the present invention is to provide a curable resin composition containing a benzoxazine resin, a varnish, a prepreg, a cured product, and a laminate or a copper-clad laminate.
  • a curable resin composition containing a maleimide resin and a benzoxazine resin of a specific structure is excellent in solvent solubility, and the cured product has heat resistance, thermal decomposition characteristics, water absorption characteristics, and dielectric properties. It has been found that the properties and chemical resistance are excellent, and the present invention has been completed.
  • n is an average value of the number of repetitions and represents a real number of 1 to 10.
  • R 1 to R 8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group If .R 3 ⁇ R 7 represent either a group is present in plural, each of R 3 ⁇ R 7 is optionally being the same or different .
  • R 9, R 10 each independently represent a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms, an aryl group, an allyl group or an alkoxy group, and when a plurality of R 9 s and R 10 s are present, each R 9 s and R 10 s may be identical to each other The dotted line may indicate that a benzene ring may be formed.
  • the curable resin composition of the present invention is excellent in solvent solubility, and the cured product is excellent in heat resistance, thermal decomposition characteristics, water absorption characteristics, dielectric characteristics, chemical resistance, and so on. It is useful for laminates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, etc.
  • the curable resin composition of the present invention contains a maleimide resin (A).
  • the maleimide resin (A) used in the present invention is a compound containing one or more maleimide groups in the molecule, and known compounds can be used. For example, aliphatic / alicyclic maleimide resin, aromatic maleimide resin and the like can be mentioned.
  • maleimide resin (A) used in the present invention include N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-hexyl maleimide, N-cyclohexyl maleimide, maleimide carboxylic acid, N-phenyl maleimide, Polyfunctional maleimide compounds obtained by the reaction of N-methylphenyl maleimide, 3,4,4'-triaminodiphenylmethane, triaminophenol etc.
  • polyaminopolymaleimide resin obtained by adding aromatic diamine to these polymaleimides can be used.
  • the novolac type maleimide resin since the novolac type maleimide resin has a molecular weight distribution, it has high varnish stability and is suitable for kneading with the benzoxazine resin. These may be commercially available ones and can also be produced using known methods.
  • a plurality of R 21 s independently exist and represent an alkyl group having 1 to 10 carbon atoms or an aromatic group, a represents 0 to 4 and b represents 0 to 3 N a is the average value of the number of repetitions and represents a real number of 1 to 5.
  • A is an alkylene group or alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond
  • R 22 is present each independently represent a hydrogen atom , An aliphatic hydrocarbon group of 1 to 5 carbon atoms or a halogen atom.
  • R 23 s independently exist and represent an alkyl group having 1 to 10 carbon atoms or an aromatic group, a represents 0 to 4 and b represents 0 to 3 N b is an average value of the number of repetitions and represents a real number of 0.01 to 8.
  • Z represents an organic group having 1 to 8 carbon atoms.
  • the GPC measurement in the present invention was performed under the following conditions.
  • the maleimide resin used in the present invention is preferably an aromatic maleimide compound, more preferably a polymaleimide represented by the above formulas (2) to (4), benzenedialdehyde and aniline from the viewpoint of heat resistance and thermal decomposition characteristics.
  • Polymaleimide polymaleimide obtained by condensation with Moreover, polyamino polymaleimide resin which made aromatic diamine be added to these polymaleimide can also be used.
  • maleimide resins may be used alone or in combination of two or more.
  • An aromatic maleimide resin and an aliphatic maleimide resin may be used in combination.
  • an aromatic maleimide resin is particularly preferable in terms of heat resistance (glass transition point) and / or elastic modulus, and a combination with a maleimide resin having two or more functional groups in one molecule is preferable.
  • the maleimide resin used in the present invention can be one having a melting point or a softening point. When it has a melting point, 200 ° C. or less is preferable, and when it has a softening point, it is preferable that it is 150 ° C. or less. If the melting point or the softening point is too high, the possibility of gelation increases during mixing, which is not preferable.
  • the curable resin composition of the present invention contains a benzoxazine resin (B) represented by the following formula (1).
  • n is an average value of the number of repetitions, and represents a real number of 1 to 10.
  • R 1 to R 8 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.
  • R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an allyl group or an alkoxy group.
  • each R 9 s and R 10 s may be the same as or different from each other.
  • the dotted line represents that a benzene ring may be formed.
  • the alkyl group having 1 to 8 carbon atoms represented by R 1 to R 8 and R 9 and R 10 in the formula (1) is not limited to any of linear, branched or cyclic alkyl group, and specific examples thereof Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n -Heptyl group, cyclopentyl group, cyclohexyl group etc. may be mentioned, and it is preferable that it is a linear or branched alkyl group having 1 to 8 carbon atoms, and is a linear or branched alkyl group having 1 to 4 carbon atoms It is more preferable that
  • the aryl group represented by R 1 to R 8 and R 9 and R 10 in the formula (1) is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon, and specific examples thereof include a phenyl group and biphenyl. Groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups and benzopyrenyl groups.
  • the alkoxy group represented by R 9 and R 10 in the formula (1) is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, sec- Examples thereof include butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, cyclopentoxy and cyclohexyloxy groups, etc., and it is a linear or branched alkoxy group having 1 to 8 carbon atoms It is preferably, and more preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • R 1 to R 8 in the formula (1) are preferably each independently a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, each independently having a hydrogen atom or a bromine atom. Or a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom is even more preferable.
  • R 9 and R 10 in the formula (1) each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, an allyl group, a linear or branched chain having 1 to 4 carbon atoms It is preferably a chain alkoxy group, more preferably a hydrogen atom, a methyl group, a phenyl group, an allyl group or a methoxy group, and still more preferably a hydrogen atom.
  • n represents the average value of the number of repetitions, and is usually a real number of 1 to 10, preferably a real number of 1 to 5.
  • the value of n can be calculated from the value of weight average molecular weight obtained by measurement of gel permeation chromatography (GPC). Specifically, it is calculated by the following formula.
  • GPC gel permeation chromatography
  • benzoxazine resin represented by the formula (1) one having a bonding position of two methylene groups bonded to the biphenyl structure in the formula (1) is 4,4 ′, that is, in the following formula (5) More preferred are the benzoxazine resins represented.
  • N and R 1 to R 10 in the formula (5) have the same meanings as n and R 1 to R 10 in the formula (1).
  • the dotted line represents that a benzene ring may be formed.
  • the benzoxazine resin represented by the formula (1) of the present invention can be prepared, for example, by using an aniline compound represented by the formula (6), a phenol compound represented by the formula (7) and an aldehyde compound as raw materials. It can be synthesized by a known method represented by the following reaction formula. Although formaldehyde is described as an example of the aldehyde compound in the reaction formula, paraformaldehyde or benzaldehyde may be used.
  • N and R 1 to R 8 in the formula (6) have the same meanings as n and R 1 to R 8 in the formula (1), and the preferred range is also the same.
  • R 9 and R 10 in the formula (7) have the same meanings as R 9 and R 10 in the formula (1), and the preferred range is also the same.
  • the dotted line represents that a benzene ring may be formed.
  • the feed ratio of the phenol compound is preferably 0.5 to 1.2 moles, and more preferably 0.75 to 1.1 moles with respect to 1 mole of the amino group of the aniline compound.
  • the preparation ratio of the aldehyde compound is preferably 1.7 to 4.3 moles, and more preferably 1.8 to 4.2 moles relative to 1 mole of the phenol compound.
  • the reaction may be carried out in a solvent or without solvent.
  • the solvent that can be used for the reaction is not particularly limited as long as it can dissolve the starting compound, and for example, methyl ethyl ketone, toluene, 1-propanol, 2-propanol, 1-butanol, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene Examples thereof include glycol monoethyl ether and ethylene glycol monobutyl ether. These solvents may be used alone or in combination.
  • the reaction temperature is preferably 60 ° C. or higher.
  • the reaction time is not particularly limited, and may be selected while confirming the progress of the reaction by confirming the residual amount of the raw material used for the reaction.
  • the benzoxazine resin can be obtained by removing the condensed water generated during the synthesis, the remaining raw materials, the solvent, etc. under reduced pressure after completion of the synthesis, but since it has self-polymerizability, it is at 160 ° C. or less Vacuum distillation is preferred.
  • the benzoxazine resin (B) used in the present invention can be one having a melting point or a softening point. When it has a melting point, 200 ° C. or less is preferable, and when it has a softening point, it is preferable that it is 150 ° C. or less. If the melting point or the softening point is too high, the possibility of gelation increases during mixing, which is not preferable.
  • n in the structural formula of the specific example has the same meaning as n in formula (1).
  • the benzoxazine resin contained in the curable resin composition of the present invention has self-curing (meaning that it can be ring-opening polymerized (cured) without other components such as a curing agent and a polymerization catalyst). That is, in addition to the fact that a curing catalyst and the like are not required at the time of curing, no by-products are generated in the polymerization process, and a polymer (cured product) with high dimensional stability without voids can be obtained.
  • the conditions for the self-curing are preferably 200 ° C. or more and several tens minutes to several hours or so.
  • the compounding ratio of the benzoxazine resin to the maleimide resin in the curable resin composition of the present invention is not particularly limited, but 0.1 to 100 parts by mass of the maleimide resin with respect to 10 parts by mass of the benzoxazine resin Is more preferably 1 to 75 parts by mass, particularly preferably 5 to 50 parts by mass.
  • the curable resin composition of the present invention can be blended with a curing catalyst, a flame retardant, a filler, an additive and the like as required.
  • the curing catalyst is not particularly limited, and known catalysts can be used. Specific examples thereof include metal complex catalysts, phosphine compounds, compounds having phosphonium salts, aromatic amine compounds, inorganic acids, inorganic bases, organic acids and organic bases.
  • metal complex catalyst generally known ones can be used.
  • metal naphthenic acid salts such as cobalt, zinc, chromium, copper, iron, manganese, nickel, titanium, acetylacetonate, salts of derivatives thereof, organic acid salts such as various carboxylate alkoxides, etc. You may mix and use.
  • Organic acid salts, chlorides, phosphates, phosphites, hypophosphites, nitrates and the like alone or in mixtures thereof may also be mentioned as an example of the metal complex catalyst.
  • phosphine compounds alkyl phosphines such as ethyl phosphine and propyl phosphine, primary phosphines such as phenyl phosphine; dialkyl phosphines such as dimethyl phosphine and diethyl phosphine, secondary phosphines such as diphenyl phosphine, methyl phenyl phosphine and ethyl phenyl phosphine; trimethyl Trialkyl phosphines such as phosphine, triethyl phosphine, tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl
  • Examples of the compound having a phosphonium salt include compounds having a tetraphenyl phosphonium salt, an alkyltriphenyl phosphonium salt and the like, and specifically, tetraphenyl phosphonium thiocyanate, tetraphenyl phosphonium tetra-p-methylphenyl borate, butyl triphenyl And phosphonium thiocyanate.
  • Examples of the aromatic amine compound include tertiary amines and imidazoles.
  • 2-ethyl-4-methylimidazole 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2- Undecylimidazole, 2-Heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 -Methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl- 4-Methylimidazole 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, diazabicycloundecene,
  • inorganic acids inorganic bases, organic acids and organic bases, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, formic acid, acetic acid, citric acid, oxalic acid P-toluenesulfonic acid, benzoic acid, phenol, allylphenol, methallylphenol, thiophenol, pyridine, trialkylamine, diazabicycloundecene, histidine and imidazoles, etc.
  • hydrochloric acid, p-toluenesulfonic acid Benzoic acid, phenol and thiophenol are preferred, and p-toluenesulfonic acid and 2-ethyl-4-methylimidazole are more preferred.
  • the compounding amount of these curing catalysts may be appropriately selected depending on the type and effects thereof, but is preferably 0.001 parts by mass or more and 10 parts by mass or less, and more preferably 100 parts by mass of the curable resin composition. It is 0.01 parts by mass or more and 5 parts by mass or less, particularly preferably 0.05 parts by mass or more and 3 parts by mass or less.
  • flame retardant examples include bromine compounds, phosphorus compounds, chlorine compounds, metal hydroxides and antimony compounds.
  • the filler include fumed silica, calcined silica, precipitated silica, crushed silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, Wax clay, kaolin clay, calcined clay, carbon black, polyamide resin, silicone resin, polytetrafluoroethylene, polybutadiene and its modified product, modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluorocarbon resin, etc. And organic or inorganic fillers of various forms. These fillers may be used alone or in combination of two or more.
  • the additive include surface treatment agents, reaction retarders, coloring materials, antistatic agents, antiaging agents, antioxidants, and the like.
  • a silane coupling agent etc. are mentioned as a specific example of a surface treating agent.
  • Specific examples of the reaction retarder include compounds such as alcohols, and examples of anti-aging agents include compounds such as hindered phenols.
  • antioxidant butyl hydroxytoluene (BHT), butyl hydroxy anisole (BHA) etc. are mentioned, for example.
  • coloring materials include titanium oxide, zinc oxide, ultramarine blue, bengala, lithopone, inorganic pigments such as lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridones Quinone pigment, dioxazine pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone pigment, iso Examples thereof include indoline pigments, organic pigments such as carbon black, and the like.
  • the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives, and the like.
  • the curable resin composition of the present invention preferably further contains a cyanate ester resin.
  • the curable resin composition of the present invention by further containing a cyanate ester resin, enables curing at a lower temperature without using the above-mentioned curing catalyst.
  • the catalyst since the catalyst is expensive, it is preferable from the viewpoint of cost to cure the curable resin composition without adding the catalyst.
  • the reliability of the resulting cured product such as heat resistance and mechanical strength is affected.
  • metal complex catalysts often used for benzoxazine resins, cyanate ester resins, and maleimide resins, which incorporate metal ion components may cause corrosion in electronic material applications.
  • the cyanate ester resin that can be used in the curable resin composition of the present invention is not particularly limited as long as it is a known cyanate ester resin, and for example, novolac type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol E type cyanate ester Resin, bisphenol type cyanate ester resin such as tetramethyl bisphenol F type cyanate ester resin; naphthol aralkyl type cyanate ester resin obtained by reaction of naphthol aralkyl type phenol resin with cyanogen halide; dicyclopentadiene type cyanate ester resin; biphenyl Alkyl-type cyanate ester resins, polycondensates of phenols with various aldehydes, polymers of phenols with various diene compounds, and phenols with ketones Cyanate ester resin obtained by reacting a condensate and polycondensates of bisphenols and various aldehydes such as cyanogen
  • phenols examples include phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene and dihydroxynaphthalene.
  • aldehydes include formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde and cinnamaldehyde.
  • Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene and the like.
  • Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and the like.
  • novolac type cyanate ester resins and naphthol aralkyl type cyanate ester resins are preferable, and novolac type cyanate ester resins are more preferable.
  • the crosslink density of the obtained cured product is increased, and not only the heat resistance is improved, but also by the improvement of the benzene concentration, excellent thermal decomposition characteristics and flame retardancy can be expected.
  • These may be used alone or in combination of two or more.
  • the lower limit value of the compounding amount is preferably 0.1 parts by mass, more preferably 1 with respect to 10 parts by mass of the benzoxazine resin from the viewpoint of heat resistance. It is part by weight, particularly preferably 3 parts by weight.
  • the upper limit value of the compounding amount is preferably 100 parts by mass, more preferably 50 parts by mass, and particularly preferably 30 parts by mass with respect to 10 parts by mass of the benzoxazine resin.
  • the curable resin composition of the present invention may contain copolymer components such as epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, polyimide resin, polyamide resin, polyurethane resin and the like. These copolymerization components may be used alone or in combination of two or more. Among these copolymerization components, it is preferable to blend an epoxy resin having reactivity with a phenolic hydroxyl group generated in the resin composition by heating, and a phenol resin, and it is particularly preferable to blend an epoxy resin.
  • copolymer components such as epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, polyimide resin, polyamide resin, polyurethane resin and the like. These copolymerization components may be used alone or in combination of two or more. Among these copolymerization components, it is preferable to blend an epoxy resin having reactivity with a phenolic hydroxyl group generated in the resin composition by heating, and a phenol resin, and it is particularly preferable to blend an
  • the epoxy resin which can be blended is not particularly limited as long as it is a compound having at least one epoxy group, and examples thereof include bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, A glycidyl ether type obtained by the reaction of an epichlorohydrin with a polyphenol such as cresol novolak, phenol novolak, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethyl bisphenol F, bixylenol, dihydroxynaphthalene, etc .; Glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexi Polyglycidyl ether type obtained by the reaction of epichlorohydrin with aliphatic polyhydric alcohol such as glycol, polyethylene
  • Glycidyl amine type and epoxidized polyolefin, glycidyl hydantoin, glycidyl alkyl hydantoin, triglycidyl cyanurate and the like. From the viewpoint of heat resistance improvement, novolac type epoxy and glycidyl amine type epoxy resins are preferable.
  • the curable resin composition of the present invention can also be used as a varnish dissolved in a solvent.
  • the use of a varnish is a preferred embodiment in that handling of the curable resin composition is facilitated.
  • a solvent which can be used for the varnish of the present invention toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, 1-propanol, 2-propanol, 1-butanol, 1, -butanol
  • 4-dioxane, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. may be mentioned, any solvent capable of dissolving the curable resin composition of the present invention may be used without particular limitation.
  • Can. The above-described additives and optional components may be blended into the varnish of the present invention as required.
  • the varnish containing the curable resin composition of the present invention is applied to various substrates, and the solvent is removed (dried) at a temperature of 150 ° C. or less, for example, and then treated at a high temperature of 200 ° C. or more
  • the base materials such as a glass nonwoven fabric
  • the varnish of this invention can also be set as fiber reinforced materials, such as a laminated board and a copper clad laminated board, using the prepreg obtained.
  • Synthesis Example 1 In a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 559 parts by mass of aniline and 500 parts by mass of toluene were charged, and 167 parts by mass of 35% hydrochloric acid was dropped over 1 hour at room temperature. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the toluene which was the organic layer was returned to the system for dehydration.
  • composition example 2 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 59 parts by mass of the aniline resin obtained in Synthesis Example 1, 28 parts by mass of phenol and 90 parts by mass of toluene were added, and the temperature was raised to 60 ° C. Then, 49 parts by mass of an aqueous solution of formaldehyde was added over 60 minutes. Thereafter, the temperature was raised to 80 ° C., and reaction was performed for 8 hours.
  • composition example 3 In the same manner as in Synthesis Example 1 except that 28 parts by mass of phenol was changed to 34 parts by mass of allylphenol, 98 parts by mass of benzoxazine resin was obtained. The softening point of the obtained benzoxazine resin was 91 ° C., and the melt viscosity was 0.5 Pa ⁇ s (150 ° C.). It was confirmed by 1 H-NMR analysis that the obtained benzoxazine resin is represented by the following formula (10). The results of 1 H-NMR are shown in FIG.
  • composition example 4 In a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 372 parts by mass of aniline and 200 parts by mass of toluene were charged, and 146 parts by mass of 35% hydrochloric acid was added dropwise over 1 hour at room temperature. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the toluene which was the organic layer was returned to the system for dehydration.
  • composition example 5 In a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 147 parts by mass of maleic anhydride and 300 parts by mass of toluene are charged and heated to azeotropically cool water and toluene After that, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution prepared by dissolving 195 parts by mass of the aromatic aniline resin (a1) obtained in Synthesis Example 4 in 195 parts by mass of N-methyl-2-pyrrolidone is kept for 1 hour while maintaining the inside of the system at 80 to 85 ° C. It dripped over.
  • the reaction is carried out at the same temperature for 2 hours, 3 parts by mass of p-toluenesulfonic acid is added, and the condensed water and toluene which are azeotroped under reflux conditions are cooled and separated to obtain toluene as an organic layer.
  • the reaction was carried out for 20 hours while dehydrating the solution.
  • 120 parts by mass of toluene was added and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and heating was performed to remove water from the system by azeotropic distillation.
  • the reaction solution was concentrated to obtain 281 parts by mass of solid maleimide resin (A1).
  • the softening point of the obtained maleimide resin was 108 ° C.
  • Example 1 45 parts by mass of the benzoxazine resin obtained in Synthesis Example 2 and 54 parts by mass of maleimide resin (manufactured by KAI / AI Kasei Co., Ltd., product name: BMI) are blended, and after kneading at 150 ° C., a curing catalyst is obtained One part by weight of 18% Octopus Zn (manufactured by Hope Pharmaceutical Co., Ltd.) was added and cured under the curing conditions of 200 ° C. ⁇ 2 hours to obtain a cured product of the present invention.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 2 A cured product of the present invention was obtained in the same manner as Example 1, except that the maleimide resin (manufactured by KAI / AI Kasei Co., Ltd. product name: BMI) was changed to the maleimide resin obtained in Synthesis Example 5.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 3 A cured product of the present invention was obtained in the same manner as in Example 1 except that the benzoxazine resin obtained in Synthesis Example 2 was changed to the benzoxazine resin obtained in Synthesis Example 3. The measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 4 55 parts by mass of the benzoxazine resin obtained in Synthesis Example 2 and 44 parts by mass of maleimide resin (manufactured by KAI / AI Kasei Co., Ltd., product name: BMI) are blended, and after kneading at 150 ° C., a curing catalyst is obtained One part by weight of 18% Octopus Zn (manufactured by Hope Pharmaceutical Co., Ltd.) was added and cured under the curing conditions of 200 ° C. ⁇ 2 hours to obtain a cured product of the present invention.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 5 A cured product of the present invention was prepared in the same manner as in Example 4 except that the curing catalyst was changed from 18% Octopus Zn (manufactured by Hope Pharmaceuticals Co., Ltd.) to 2-ethyl 4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.). Obtained.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 6 55 parts by mass of the benzoxazine resin obtained in Synthesis Example 2 and 45 parts by mass of maleimide resin (manufactured by KAI / AI Kasei Co., Ltd., product name: BMI) are blended, and after kneading at 150 ° C., 200 ° C. ⁇ 2 It was cured under the curing conditions of time + 230 ° C. ⁇ 2 hours to obtain a cured product of the present invention.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 7 55 parts by mass of the benzoxazine resin obtained in Synthesis Example 2 and 45 parts by mass of bis-3-ethyl-5-methyl-4-maleimidophenylmethane (manufactured by Kei Ikasei Co., Ltd., product name: BMI-70) After blending in parts and kneading at 150 ° C., curing was carried out under the curing conditions of 200 ° C. ⁇ 2 hours + 230 ° C. ⁇ 2 hours to obtain a cured product of the present invention. The measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 8 55 parts by mass of the benzoxazine resin obtained in Synthesis Example 2, 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (manufactured by KAI / AI KASEI CO., LTD., Product name: BMI-80) 45 parts by mass of K) were kneaded at 150 ° C., and then cured under the curing conditions of 200 ° C. ⁇ 2 hours + 230 ° C. ⁇ 2 hours to obtain a cured product of the present invention.
  • the measurement results of the physical properties of the cured product are shown in Table 1.
  • Example 9 50 parts by mass of the benzoxazine resin obtained in Synthesis Example 2, 50 parts by mass of the maleimide resin obtained in Synthesis Example 5, 0.5 parts by mass of 18% Octopus Zn (manufactured by Hope Pharmaceutical Co., Ltd.), 100 parts by mass of MEK Parts were added and the mixture was stirred under reflux at 30 ° C. to form a varnish of the present invention.
  • the obtained varnish was impregnated into glass cloth (product name: 1031 NT-105, manufactured by Arisawa Mfg. Co., Ltd.), dried in an oven at 80 ° C., and additionally dried at 150 ° C. to obtain a prepreg of the present invention.
  • Example 10 10 parts by mass of the benzoxazine resin obtained in Synthesis Example 2, 30 parts by mass of the maleimide resin obtained in Synthesis Example 5, 2,2-bis (4-cyanatophenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.) 60 parts by mass) were mixed while heating and melting at 120 ° C. to obtain a benzoxazine-maleimido-cyanate ester resin composition.
  • MDSC measurement was performed to confirm the curing behavior of the obtained resin composition. The results of the MDSC measurement are shown in FIG. Further, the obtained resin composition was transfer molded under the conditions of 200 ° C. and a molding pressure of 50 kg / cm 2 , and the molded body was post-cured at 220 ° C. to obtain a cured product of the present invention.
  • the measurement results of the physical properties of the cured product are shown in Table 3.
  • Example 1 A cured product was obtained in the same manner as in Example 4, except that the benzoxazine resin obtained in Synthesis Example 2 was changed to a bisphenol F-type benzoxazine resin (manufactured by Shikoku Kasei Co., Ltd.). The measurement results of the physical properties of the cured product are shown in Table 1.
  • Comparative example 2 65 parts by mass of bisphenol A type epoxy resin (product name: JER-828, manufactured by Mitsubishi Chemical Corporation), 50 parts by mass of phenol novolac (product name: H-1, manufactured by Meiwa Kasei Co., Ltd.), 2-ethyl 0.5 parts by mass of -4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.), 70 parts by mass of MEK and 30 parts by mass of methyl cellosolve were added, and the mixture was stirred under reflux at 30 ° C. to prepare a varnish.
  • the varnish was impregnated into glass cloth (product name: 1031 NT-105, manufactured by Arisawa Seisakusho Co., Ltd.), dried in an oven at 80 ° C., and additionally dried at 150 ° C. to obtain a prepreg.
  • Four sheets of the obtained prepreg are laminated and sandwiched between copper foils (product name: CF-T9FZ-HTE-18, manufactured by Fukuda Metal Foil Division Co., Ltd.), and subjected to 200 ° C ⁇ 2 hours + 230 ° C ⁇ 2 hours vacuum press It hardened on the hardening conditions of, and obtained the copper-clad laminate board.
  • the obtained copper-clad laminate was attached to a 25% iron (III) chloride solution to obtain a laminate in which the copper-clad laminate was dissolved.
  • the obtained laminate was subjected to the acid resistance test, the alkali resistance test, and the etching grade measurement for the desmear solution. The results are shown in Table 2.
  • the obtained cured product was measured under the following conditions. ⁇ Heat resistance> -Measurement of Tg (temperature at maximum of tan ⁇ ) was performed by DMA measurement.
  • Measuring device Dynamic viscoelasticity measuring instrument TA-instruments, Q-800 Measurement temperature: 30 to 350 ° C Heating rate: 2 ° C / min
  • Sample size Width 5 mm ⁇ length 50 mm ⁇ thickness 0.8 mm ⁇ Dielectric constant and dielectric loss tangent> -Measurement was performed by a cavity resonator perturbation method using a cavity resonator.
  • Measurement device Cavity resonator Agilent Technologies, Inc.
  • Measurement method Measurement at 1 GHz according to JIS K6991 Measurement mode: Cavity resonator perturbation method Measurement temperature: 25 ° C.
  • the obtained laminate was measured under the following conditions.
  • ⁇ Acid resistance test> ⁇ Adjust hydrochloric acid specified in JIS K 8576 to an aqueous solution with a concentration of 3 ⁇ 0.2 wt% and a temperature of 40 ⁇ 2 ° C, immerse the sample for 24 hours, remove it, and immediately wash in running water for 20 ⁇ 10 minutes, Check for swelling or discoloration of the dry, clean sample.
  • ⁇ Alkali resistance test> -Adjust sodium hydroxide specified in JIS K 8576 to an aqueous solution with a concentration of 3 ⁇ 0.2 wt% and a temperature of 40 ⁇ 2 ° C, immerse the sample for 24 hours, and then immediately take out it for 20 ⁇ 10 minutes in running water.
  • the curing behavior of the resin composition obtained in Example 10 and Comparative Examples 4 and 5 was measured under the following conditions. ⁇ Hardening behavior> The heat of curing was observed by MDSC measurement. Measuring device: Q-2000 TA Instruments Co. Measuring temperature: 25 to 330 ° C Heating rate: 3 ° C / min Measurement mode: MDSC measurement
  • Tg 1st First measurement result
  • Tg 2nd After completion of the first measurement, the sample heated to 350 ° C. is cooled to room temperature and re-measured result ⁇ Tg: (Tg 2nd)-(Tg 1st)
  • Comparative Example 1 was good in heat resistance, but failed in other characteristics.
  • the curable resin compositions (Examples 1 to 8) of the present invention showed excellent results in all of the heat resistance, thermal decomposition characteristics, dielectric characteristics, and water absorption characteristics.
  • Comparative Example 3 did not dissolve in MEK generally used in the field of substrates, whereas Example 9 had good solubility in MEK and was excellent in processability to laminates.
  • Example 9 was excellent in chemical resistance, and showed a result of being more excellent in the resistance to desmear liquid than Comparative Example 2 which is a general epoxy laminate.
  • Example 10 adds a benzoxazine resin of the present invention, although a cyanate ester resin is not added. And promoting the polymerization of the maleimide resin. Furthermore, from the results in Table 3, it was confirmed that the benzoxazine-maleimido-cyanate ester resin composition of the present invention hardly causes a change in ⁇ Tg and cures under the condition of 220 ° C. Moreover, the cured product was excellent in heat resistance and showed excellent results as compared with the composition of BT resin known as a low dielectric material. Since Example 10 is cured without a catalyst and is excellent in heat resistance and low dielectric property, industrial applicability is high.
  • the curable resin composition of the present invention is excellent in solvent solubility, and a cured product excellent in heat resistance, thermal decomposition characteristics, dielectric characteristics, water absorption characteristics, and chemical resistance can be obtained. It is useful for sealing material applications, laminates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, etc.

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Abstract

L'invention concerne une composition de résine durcissable qui présente une excellente solubilité dans les solvants et permet d'obtenir un produit durci qui présente une excellente résistance à la chaleur, de remarquables caractéristiques en matière de décomposition thermique, de remarquables caractéristiques diélectriques et de remarquables caractéristiques en matière d'absorption d'eau, ainsi qu'une très grande résistance aux agents chimiques, et qui est appropriée pour un matériau composite renforcé de fibres qui est utilisé dans des circuits imprimés pour dispositifs électroniques ou dans le domaine de l'aéronautique. L'invention concerne ainsi une composition de résine durcissable qui contient (A) une résine maléimide et (B) une résine benzoxazine qui est représentée par la formule (1). (Dans la formule (1), n représente le nombre moyen de répétitions, qui est un nombre réel de 1 à 10; chacun des R1 à R8 représente indépendamment un atome d'hydrogène, un atome d'halogène, un groupe alkyle comportant de 1 à 8 atomes de carbone ou un groupe aryle; dans le cas de la présence d'une pluralité de chacune des fractions R3 à R7, les fractions R3 à R7 peuvent être, respectivement, identiques ou différentes les unes des autres; chacun des R9 et R10 représente indépendamment un atome d'hydrogène, un groupe alkyle comportant de 1 à 8 atomes de carbone, un groupe aryle, un groupe allyle ou un groupe alcoxy; dans le cas de la présence d'une pluralité de chacune des fractions R9 et R10, les fractions R9 et R10 peuvent, respectivement, être identiques ou différentes les unes des autres; et les lignes pointillées indiquent qu'un cycle benzénique peut être formé.)
PCT/JP2018/038852 2017-10-20 2018-10-18 Composition de résine durcissable, vernis, préimprégné, produit durci, stratifié et stratifié recouvert de cuivre WO2019078300A1 (fr)

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CN112142682A (zh) * 2020-10-14 2020-12-29 广东同宇新材料有限公司 联苯型苯并噁嗪及其制备方法与聚苯并噁嗪树脂

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