WO2022054614A1 - Method for producing aromatic ether compound having vinyl group - Google Patents

Method for producing aromatic ether compound having vinyl group Download PDF

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Publication number
WO2022054614A1
WO2022054614A1 PCT/JP2021/031623 JP2021031623W WO2022054614A1 WO 2022054614 A1 WO2022054614 A1 WO 2022054614A1 JP 2021031623 W JP2021031623 W JP 2021031623W WO 2022054614 A1 WO2022054614 A1 WO 2022054614A1
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Prior art keywords
group
compound
vinyl
vinyl group
reaction
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PCT/JP2021/031623
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French (fr)
Japanese (ja)
Inventor
次俊 和佐野
一男 石原
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日鉄ケミカル＆マテリアル株式会社
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Application filed by 日鉄ケミカル＆マテリアル株式会社 filed Critical 日鉄ケミカル＆マテリアル株式会社
Priority to JP2022547506A priority Critical patent/JPWO2022054614A1/ja
Priority to CN202180061698.6A priority patent/CN116075529A/en
Priority to KR1020237006011A priority patent/KR20230042487A/en
Publication of WO2022054614A1 publication Critical patent/WO2022054614A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • 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
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings

Definitions

  • the present invention relates to a method for producing an aromatic ether compound having a vinyl group obtained by reacting a compound having a phenolic hydroxyl group with vinyl aralkyl halide, improving the reactivity and facilitating the removal of by-products salts.
  • the present invention relates to a method for producing an aromatic ether compound having a vinyl group, which can obtain a desired product in a high yield.
  • Patent Document 1 proposes N, N dimethylformamide as a solvent, and Patent Document 3 proposes a monohydric alcohol or a glycol solvent.
  • Patent Document 4 proposes a ketone solvent that is sparingly soluble in water
  • Patent Document 5 proposes an aprotonic polar solvent composed of dimethylsulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, and propylene carbonate.
  • solubility may differ depending on the structure of the phenol compound to be reacted, many improvements in reactivity with solvent species have been investigated, but the optimum solvent has not yet been found.
  • the present invention uses a method for finding a suitable solvent and increasing the reaction rate in the method for producing an ether compound having a vinyl group obtained by reacting a compound having a phenolic hydroxyl group with a vinyl aralkyl halide, which has been studied so far. Further, the present invention finds an efficient salt removing method and provides a more efficient production method than the conventional one.
  • the present invention is a method for producing an ether compound having a vinyl group, wherein a compound having a phenolic hydroxyl group and a vinyl aralkyl halide represented by the following general formula (1) are based on an alkali (earth).
  • an aromatic having a vinyl group is characterized in that the reaction is carried out using a reaction solvent containing 50% by mass or more of diethylene glycol dimethyl ether.
  • This is a method for producing a group ether compound.
  • Ar 1 is an aromatic ring group and X is a halogen atom.
  • the alkali (earth) metal compound is a solid alkali (earth) metal hydroxide or an alkali (earth) metal carbonate, and the reaction is preferably carried out in a non-aqueous system, and the solid alkali (earth) is preferable.
  • the metal compound it is preferable to carry out the reaction in an inert gas atmosphere, and it is possible to wash with water after removing the alkali halide (earth) metal generated by the reaction by filtration. preferable.
  • the compound having a phenolic hydroxyl group is preferably a phenol compound having two or more phenolic hydroxyl groups.
  • the present invention is a composition containing an aromatic ether compound having a vinyl group obtained by the above-mentioned production method and a radical initiator as essential components, and is a cured product obtained by curing the composition.
  • a vinyl group-containing aromatic ether compound obtained by the above-mentioned production method can be obtained, and a radical initiator is blended with the vinyl group-containing aromatic ether compound as an essential component to prepare a resin composition.
  • a method for producing an aromatic ether-based resin which comprises radically polymerizing a contained aromatic ether compound or resin composition.
  • a fibrous base material is blended with the vinyl group-containing aromatic ether compound or resin composition and semi-cured.
  • a method for producing a prepreg which comprises applying the vinyl group-containing aromatic ether compound or resin composition to a resin film, and a method for producing a resin sheet, which comprises semi-curing the prepreg and / or a resin thereof. This is a method for manufacturing a laminated board formed by laminating sheets.
  • vinyl aralkyl halide is efficiently produced by reacting a compound having a phenolic hydroxyl group with vinyl aralkyl halide using diethylene glycol dimethyl ether as an essential component as a reaction solvent. It can react with a compound having a phenolic hydroxyl group, can efficiently remove by-produced salts, and can obtain the desired vinyl group-containing aromatic ether compound in high yield.
  • the method for producing an aromatic ether compound having a vinyl group (hereinafter, also referred to as a vinyl compound) of the present invention comprises a compound having a phenolic hydroxyl group (hereinafter, also referred to as a phenol resin) and a vinyl aralkyl halide (hereinafter, also referred to as an aromatic vinyl agent). Also referred to as), the reaction is characterized by using 50% by mass or more of diethylene glycol dimethyl ether as the reaction solvent. At that time, it is preferable to carry out the operation in an inert gas atmosphere, and it is preferable to use a solid alkali (earth) metal compound in a non-aqueous system.
  • a solid alkali (earth) metal compound in a non-aqueous system.
  • the compound having a phenolic hydroxyl group that can be used in the present invention is not particularly limited, and examples thereof include known compounds, preferably compounds having two or more phenolic hydroxyl groups.
  • mononuclear phenol compounds such as hydroquinone, resorcinone, catechol, dibutylhydroquinone, and fluoroglycinol, bisphenol A, bisphenol F, tetramethylbisphenol F, biphenol, tetramethylbiphenol, bisphenol sulfone, bisphenol sulfide, Dinuclear phenol compounds such as naphthalenediol, bisphenol fluorene and compounds having their isomers and substituents, phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, aralkylphenol resin, aralkylnaphthol resin, aralkylbisphenol.
  • Phenolic resins composed of phenols bonded with a xylylene structure such as resins, phenolic resins composed of phenols bonded with a bismethylbiphenyl structure Trishydroxyphenylmethane type novolak resin, dicyclopentadiene type phenol resin and international release Polyfunctional phenolic resins such as the compounds of No.
  • Ar 1 is an aromatic ring group, preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
  • This aromatic ring group is unsubstituted or, as a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
  • the alkyl group or alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-pentyl group.
  • n-hexyl group isopropyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group , N-pentyloxy group, n-hexyloxy group, isopropoxy group, sec-butoxy group, t-butoxy group, isopentyloxy group, neopentyloxy group, t-pentyloxy group, isohexyloxy group, cyclopentyloxy Groups, cyclohexyloxy groups and the like can be mentioned.
  • Examples of the aryl group or aryloxy group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, an ethylphenyl group, an o-xysilyl group, a propylphenyl group, a mesityl group, a naphthyl group, an indanyl group, a phenoxy group, a tolyloxy group and an ethyl.
  • Examples thereof include a phenoxy group, a xylyloxy group, a propylphenoxy group, a mesityloxy group, a naphthyloxy group and the like.
  • Examples of the aralkyl group or aralkyloxy group having 7 to 11 carbon atoms include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a phenethyl group, a 1-phenylethyl group, a 2-phenylisopropyl group, a naphthylmethyl group and a benzyl group.
  • Examples thereof include an oxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a phenethyloxy group, a 1-phenylethyloxy group, a 2-phenylisopropyloxy group, and a naphthylmethyloxy group.
  • Examples of the vinyl aralkyl halide include chloromethylstyrene, bromomethylstyrene, chloromethylnaphthylene, bromomethylnaphthylene, and compounds having isomers and substituents thereof.
  • the substitution position of the vinyl group for example, in the case of vinylbenzyl halide, the 4-position is preferable, and the 4-position is more preferably 50 mol% or more of the whole. Specific examples thereof include, but are not limited to, p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, etc., and may be used alone.
  • CMS-14 manufactured by AGC Seimi Chemical Co., Ltd., a mixture of about 95/5 of p-vinylbenzyl chloride and m-vinylbenzyl chloride
  • CMS-P manufactured by AGC Seimi Chemical Co., Ltd., p-
  • the compounding ratio of the compound having a phenolic hydroxyl group and the vinyl aralkyl halide is preferably 0.80 to 4.0 mol of vinyl aralkyl halide with respect to 1 mol of the hydroxyl group in the compound having a phenolic hydroxyl group. 95 to 2.0 mol is more preferable, and 1.0 to 1.5 mol is further preferable. If the amount of vinyl aralkyl halide is less than 0.80 mol, the number of residual hydroxyl groups increases and the heat resistance decreases with respect to 1 mol of the compound having a phenolic hydroxyl group, and if it exceeds 4.0 mol, unreacted vinyl aralkyl. There is too much residual halide or too much side reaction polymer.
  • diethylene glycol dimethyl ether is used as the reaction solvent.
  • the amount of diethylene glycol dimethyl ether is 50% by mass or more, preferably 80% by mass or more, and more preferably 100% by mass (single use) with respect to the total solvent.
  • the solvent that can be used in combination is not particularly limited, but a non-aqueous solvent is preferable.
  • a non-aqueous solvent is preferable.
  • hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, penten, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, propanol, butanol, amyl alcohol, pentanol, hexanol, methyl amyl alcohol.
  • Examples thereof include, but are not limited to, acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, and dimethyl sulfoxide.
  • a solvent capable of separating the aqueous layer For example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and the like can be mentioned.
  • the production method of the present invention preferably reacts in an atmosphere of an inert gas.
  • the active gas include nitrogen and argon.
  • Oxygen is often used in the synthesis of vinyl compounds in order to suppress the polymerization reaction of vinyl groups, but the oxidation of phenol groups may occur and the reactivity with vinyl aralkyl halide may decrease. Therefore, it is preferable to react in an inert gas atmosphere.
  • the reaction is carried out in the presence of an alkali metal compound or an alkaline earth metal compound showing basicity.
  • the alkaline (earth) metal means an alkali metal, an alkaline earth metal, or both. It is preferable to react with a solid basic alkaline (earth) metal compound.
  • the solid alkali (earth) metal compound reacts with the halogen of the raw material vinyl aralkyl halide to promote the reaction with a compound having a phenolic hydroxyl group such as a phosphorus-containing phenol resin.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • Alkaline compounds such as hydroxides of the above can be mentioned, and alkali (earth) metal hydroxides or alkali metal carbonates are preferable from the viewpoint of promoting the reaction. Further, it may be used alone or in combination of two or more. Since it is preferable to carry out the reaction in a non-aqueous system from the viewpoint of improving the yield, it is preferable to use it as a solid.
  • the amount of the alkaline (earth) metal compound used is 0.5 to 5.0 mol, preferably 1 to 3 mol, and 1.2 to 3 mol, relative to 1 mol of vinyl aralkyl halide in the case of alkali metal hydroxide. 2 mol is more preferred. If this amount is less than 0.5 mol, the reaction will not be sufficient. On the other hand, if it exceeds 5.0 mol, a large amount of acid required for neutralization is required, which is economically unfavorable. In the case of alkaline earth metal hydroxide or alkali metal carbonate, 1/2 times the above mole is suitable.
  • the pH in the system can be confirmed by adding water to the sample in the system and using pH test paper. It is desirable to adjust the number of divisions and the timing of addition so as to maintain pH 10 or less, more preferably pH 9 or less.
  • the reaction is carried out at pH 11 or higher, when a phosphorus-containing phenol compound is used as the phenolic hydroxyl group, some phosphorus-containing phenol compounds undergo a decomposition reaction, and a desired compound cannot be obtained, resulting in a yield. Will lead to deterioration of.
  • the reaction contains water in the system, the decomposition reaction is accelerated, so that it is preferable to react in a non-aqueous system. Further, by carrying out the reaction in a non-aqueous system, the reaction solvent diethylene glycol dimethyl ether can be easily recycled, which is economically advantageous.
  • the reaction temperature is preferably 30 to 150 ° C, more preferably 40 to 100 ° C, still more preferably 50 to 90 ° C. If the reaction temperature is high, polymerization will occur due to the reaction of vinyl groups, and if it is too low, the reaction will not proceed and the efficiency will be poor.
  • the reaction can be confirmed by tracking the consumption of the alkali metal compound by pH, tracking the residual amount of vinyl aralkyl halide by various chromatographies, IR, UV, or the like. For example, the end point can be determined by measuring the residual amount of vinyl aralkyl halide as a raw material and the peak of the functional group involved in the reaction.
  • the reaction may be carried out in the presence of a polymerization inhibitor.
  • a polymerization inhibitor By adding a polymerization inhibitor, it is possible to prevent the vinyl aralkyl halide used in the reaction or the vinyl group-containing aromatic ether compound which is the target product from polymerizing to form an oligomer as a by-product.
  • Known polymerization inhibitors can be used without limitation, and organic compounds such as hydroquinone, hydroxymonomethyl ether, t-butylcatechol, t-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine can be used.
  • copper compounds such as copper chloride and copper sulfide may be mentioned, and these may be used in combination.
  • the reaction can be completed within 10 hours, more preferably within 7 hours, without leaving the raw material vinyl aralkyl halide.
  • Alkaline (earth) metal halides as by-products can also be easily removed by filtration and washing with water, and the chlorine ions in the aqueous layer in washing with water can be reduced to preferably 100 ppm or less, more preferably 30 ppm or less.
  • the yield of the vinyl compound thus obtained is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.
  • reaction solution (reaction mixture) is subjected to distillation of the reaction solvent, solvent substitution, etc., if necessary, and washing with water or the like, activated charcoal treatment, silica gel chromatography, or the like is used.
  • the desired vinyl group-containing aromatic ether compound can be extracted by purification.
  • the vinyl group-containing aromatic ether compound obtained by the production method of the present invention has a vinyl equivalent of 100 to 500 g / eq. Is preferable, and more preferably 200 to 300 g / eq.
  • the total amount of chlorine is preferably 3000 ppm or less, more preferably 2000 ppm or less.
  • a phosphorus-containing phenolic resin suitable as a compound having a phenolic hydroxyl group is represented by the above general formula (2).
  • R 1 and R 2 are hydrocarbon groups that may independently have oxygen atoms having 1 to 15 carbon atoms, and may be linear, branched, or cyclic, and have an aromatic fragrance.
  • a group having a group ring structure is preferable, and R 1 and R 2 may form a cyclic structure.
  • Hydrocarbon groups that may have an oxygen atom having 1 to 15 carbon atoms include, for example, a linear or branched alkyl group having 1 to 15 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms, or a branched hydrocarbon group.
  • Examples thereof include a chain or a cyclic or alkoxy group, an aryl group having 6 to 15 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aralkyloxy group having 7 to 15 carbon atoms, and the like. ..
  • the aromatic ring may have a substituent having 1 to 9 carbon atoms.
  • substituent having 1 to 9 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, and an aryloxy group having 6 to 9 carbon atoms. Examples thereof include an arylyl group having 7 to 9 carbon atoms and an aralkylyloxy group having 7 to 9 carbon atoms.
  • the oxygen atom can be contained between the carbons constituting the hydrocarbon chain or the hydrocarbon ring.
  • the Ar 2 is an aromatic ring group and has a structure derived from the raw material quinone compound.
  • the aromatic ring group include a benzene ring group, a naphthalene ring group, a biphenyl ring group, a terphenyl ring group and the like, and a benzene ring group or a naphthalene ring group is preferable.
  • This aromatic ring group may be unsubstituted or may have a substituent exemplified by Ar 1 above.
  • Examples of the phosphorus-containing phenol resin include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (for example, HCA-HQ, manufactured by Sanko Chemical Co., Ltd.), 10 -(2,7-Dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (eg, HCA-NQ, manufactured by Sanko Kagaku Co., Ltd.), 10- (2,5-dihydroxyphenyl)- 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- [2- (dihydroxynaphthyl)]-8-benzyl-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxy
  • a catalyst can be used for the reaction if necessary.
  • the catalyst used include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide, triphenylphosphine, and tris (2).
  • phosphines such as phosphine, phosphonium salts such as benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutylphosphonium iodide, 2-methylimidazole, 2-ethyl- Examples thereof include various catalysts such as imidazoles such as 4-methylimidazole, but the present invention is not limited to these, and they may be used alone or in combination of two or more. The amount of the catalyst used is 10 parts by mass or less with respect to 100 parts by mass of the raw material.
  • the vinyl group-containing aromatic ether compound obtained by the production method of the present invention can be made into a resin or a cured resin product.
  • the resin composition of the present invention contains a vinyl group-containing aromatic ether and a radical initiator as essential components. This resin composition may or may not contain a resin, and if it does not contain the resin, it becomes a resin precursor.
  • a radical initiator is blended in the resin composition of the present invention.
  • the radical initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetate peroxide, acetyl acetone peroxide, cumene hydroperoxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-.
  • the resin composition of the present invention can be blended with various curable resins, thermoplastic resins or other polymerizable compounds.
  • curable resin or other polymerizable compound that gives the curable resin examples include unsaturated polyester resin, curable maleimide resin, polycyanate resin, phenol resin, and one or more polymerizable unsaturated hydrocarbon groups in the molecule.
  • One or more vinyl compounds having one or more can be mentioned. 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 type is not particularly limited. That is, the vinyl compounds may be any one that can be cured by forming a crosslink by reacting with the vinyl compound of the present invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and 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 per molecule of such vinyl compounds (also referred to as the number of polymerizable double bonds) varies depending on the Mw of the vinyl compounds, but is, for example, 1 to 20. It is preferable that the number is 2, and the number is more preferably 2 to 18. If the number of the polymerizable double bonds is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. On the other hand, if this amount is too large, the reactivity becomes too high, and there is a possibility that problems such as a decrease in storage stability of the composition and a decrease in the fluidity of the composition may occur.
  • vinyl compounds examples include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ether (PPE) having a terminal modified with a (meth) acryloyl group or a styryl group, and (meth) acryloyl in the molecule.
  • TAIC triallyl isocyanurate
  • PPE modified polyphenylene ether
  • Polyfunctional (meth) acrylate compounds having two or more groups vinyl compounds having two or more vinyl groups in the molecule (polyfunctional vinyl compounds) such as polybutadiene, and vinyl benzyl compounds such as styrene and divinylbenzene. And so on.
  • those having two or more carbon-carbon double bonds in the molecule are preferable, and specifically, TAIC, a polyfunctional (meth) acrylate compound, a modified PPE resin, a polyfunctional vinyl compound, and a divinylbenzene compound. And so on.
  • TAIC a polyfunctional (meth) acrylate compound
  • modified PPE resin a polyfunctional vinyl compound
  • divinylbenzene compound a divinylbenzene compound.
  • cross-linking is more preferably formed by the curing reaction, and the heat resistance of the cured product of the resin composition can be further enhanced.
  • these may be used alone or in combination of two or more.
  • a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination. Examples of the compound having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
  • thermoplastic resin examples include polystyrene, polyphenylene ether resin, polyetherimide resin, polyether sulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin and the like, and known thermoplastic elastomers (for example, styrene-).
  • Ethylene-propylene copolymer styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.
  • Rubbers eg, polybutadiene, polyisoprene
  • a filler can be added to the resin composition of the present invention.
  • the filler include those added to enhance the heat resistance and flame retardancy of the cured product of the resin composition, and known fillers can be used, but the filler is not particularly limited. Further, by containing a filler, heat resistance, dimensional stability, flame retardancy and the like can be further improved. Specifically, silica such as spherical silica, alumina, titanium oxide, metal oxides such as mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, etc.
  • Examples thereof include glass powder, silica balloon, aluminum borate, barium sulfate, calcium carbonate, etc., glass fiber, pulp fiber, synthetic fiber, ceramic fiber, etc., but are not limited thereto, and may be used alone. Two or more types may be used in combination. Further, a pigment or the like may be blended. When a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retardant aid, and flame retardancy can be ensured even if the phosphorus content is low. Among these, silica, mica, and talc are preferable, and spherical silica is more preferable. Further, one of these may be used alone, or two or more thereof may be used in combination.
  • a metal hydroxide such as aluminum hydroxide or magnesium hydroxide
  • the filler may be used as it is, or may be surface-treated with a silane coupling agent such as an epoxy silane type or an amino silane type.
  • a silane coupling agent such as an epoxy silane type or an amino silane type.
  • a vinylsilane type, a methacrylate silane type, an acryloxysilane type, and a styrylsilane type silane coupling agent are preferable from the viewpoint of reactivity with a radical initiator.
  • the adhesive strength with the metal foil and the interlayer adhesive strength between the resins are increased.
  • the silane coupling agent may be added and used by the integral blend method.
  • the content of the filler is preferably 10 to 200 parts by mass with respect to a total of 100 parts by mass of the solid content excluding the filler (including organic components such as monomers and flame retardants and excluding the solvent). It is preferably 30 to 150 parts by mass.
  • the resin composition of the present invention may further contain additives other than the above.
  • additives include dispersion of defoaming agents such as silicone-based defoaming agents and acrylic acid ester-based defoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and wet dispersants. Agents and the like can be mentioned.
  • Molded products or cured products obtained by polymerizing, curing or molding the resin composition of the present invention are molded products and laminated products for various purposes. It can be used as an object, a cast object, an adhesive, a coating film, and a film.
  • the cured product of the semiconductor encapsulation material is a cast product or a molded product, and as a method for obtaining a cured product for such an application, the resin composition is cast or molded using a transfer molding machine, an injection molding machine, or the like. Further, the cured product can be obtained by further heating at 80 to 230 ° C. for 0.5 to 10 hours.
  • the resin composition of the present invention can also be used as a prepreg.
  • a prepreg When manufacturing a prepreg, it is prepared in the form of a varnish for the purpose of impregnating the base material (fibrous base material) for forming the prepreg or for the purpose of using it as a circuit board material for forming a circuit board, and using a resin varnish. can do.
  • This resin varnish is suitable for circuit boards and can be used as a varnish for circuit board materials.
  • Specific examples of the use of the circuit board material referred to here include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.
  • the organic solvent used for the resin varnish is not particularly limited as long as it does not inhibit the curing reaction.
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; polar solvents such as dimethylacetamide and dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene. It is also possible to use one kind or a mixture of two or more kinds of these. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.
  • the amount of the organic solvent used in preparing the resin varnish is preferably 5 to 900% by weight, more preferably 10 to 700% by weight, and particularly preferably 20 with respect to 100% by weight of the resin composition of the present invention. ⁇ 500% by weight.
  • a known material is used as the base material used to prepare the prepreg.
  • base materials such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper are used individually or in combination of two or more.
  • a coupling agent can be used for these base materials for the purpose of improving the adhesiveness at the interface between the resin and the base material.
  • general agents such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used.
  • Examples of the method for obtaining the prepreg include a method in which the base material is impregnated with the resin varnish and then dried. Impregnation is performed by dipping, coating, or the like. The impregnation can be repeated multiple times as needed, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust to the desired resin composition and amount. It is possible. After impregnation, a prepreg can be obtained by heating and drying at 100 to 180 ° C. for 1 to 30 minutes.
  • the amount of resin in the prepreg is preferably 30 to 80% by weight of the resin content.
  • the composition of the present invention can also be used as a laminated board.
  • a laminated board When forming a laminated board using a prepreg, one or a plurality of prepregs are laminated, and metal foils are arranged on one side or both sides to form a laminated product, and the laminated material is heated and pressed to integrate the laminated sheets. do.
  • the metal foil a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used.
  • As a condition for heating and pressurizing the laminate it is sufficient to appropriately adjust and heat and pressurize under the condition that the resin composition is cured, but if the pressurizing pressure is too low, air bubbles remain inside the obtained laminate.
  • the temperature can be set to 180 to 250 ° C.
  • the pressure can be set to 49.0 to 490.3 N / cm 2 (5 to 50 kgf / cm 2 ), and the heating and pressurizing time can be set to 40 to 240 minutes.
  • a multilayer plate can be produced by using the single-layer laminated plate thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material.
  • An insulating layer is formed from a resin sheet, a metal foil with resin, or a prepreg on the circuit forming surface on one side or both sides of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate. It is a thing.
  • the vinyl curable composition of the present invention can also be used for the build-up film.
  • the method for producing a build-up film from the resin composition of the present invention include a method in which the resin varnish is applied onto a support film and dried to form a film-shaped insulating layer.
  • the film-shaped insulating layer thus formed can be used as a build-up film for a multilayer printed wiring board.
  • the cured product of the resin composition containing the vinyl compound obtained by the production method of the present invention has a total chlorine of 3000 ppm or less, no halogen dissociation at high temperature, a low dielectric constant of 3.2 or less, and 0.006 or less. It shows low dielectric loss tangent and has excellent heat resistance. In particular, when a phosphorus-containing phenol resin is used as the compound having a phenolic hydroxyl group, flame retardancy is also exhibited.
  • Hydroxy group equivalent Measured according to JIS K 0070 standard. Specifically, using a potentiometric titrator, 1,4-dioxane is used as a solvent, acetylation is performed with 1.5 mol / L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol / L-. Titration was performed using potassium hydroxide. Unless otherwise specified, the hydroxyl group equivalent of the phenol resin means the phenolic hydroxyl group equivalent.
  • the vinyl aralkyl halides and compounds having a phenolic hydroxyl group used in the following examples are as follows.
  • -CMS Chloromethylstyrene, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., CMS-P)
  • PN Phenolic novolak resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., SP-2060, hydroxyl group equivalent 105 g / eq., Softening point 85 ° C)
  • DOPO-NQ 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA-NQ, phosphorus content 8.3%)
  • Example 1 97.9 parts of PN and 229 parts of diethylene glycol dimethyl ether were placed in a 4-port separable flask equipped with a stirrer, a purge gas inlet, a thermometer, and a cooling tube, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream to dissolve the flask. .. Subsequently, 148.1 parts of CMS was charged, and 57.5 parts of solid potassium hydroxide was divided into 6 parts to carry out the reaction while keeping the temperature at 70 ° C. to 75 ° C. A sample was taken before adding potassium hydroxide, water was added, and the pH in the system was confirmed with pH test paper.
  • Example 2 In Example 1, the reaction was carried out under an air flow, and the same operation was performed except that a 50% aqueous potassium hydroxide solution was used instead of the solid potassium hydroxide. The reaction time was 10 hours.
  • the vinyl equivalent of the obtained vinyl compound (A-2) was 241 g / eq, the total chlorine was 1420 ppm, and the yield was 71%.
  • Example 3 The same equipment as in Example 1 except that DOPO-NQ 124.1 parts, diethylene glycol dimethyl ether 126.7 parts, CMS 129.6 parts, solid potassium hydroxide 83.3 parts, and toluene 521.3 parts were used instead of PN. I did a lot of operations. After confirming that there was no residual CMS, the reaction was terminated. The reaction was 7 hours. Since the chlorine ion in the water layer in the second water washing was 5 ppm or less, the water washing was completed. Dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (B-1). The vinyl equivalent of the obtained vinyl compound (B-1) was 275 g / eq, the total chlorine was 1330 ppm, and the yield was 84%.
  • Example 4 In Example 3, the same operation was carried out except that 91 parts of diethylene glycol dimethyl ether and 39 parts of toluene were used instead of diethylene glycol dimethyl ether alone as the solvent. After confirming that there was no residual CMS, the reaction was terminated. The reaction was 9 hours. Since the chlorine ion in the water layer in the second water washing was 5 ppm or less, the water washing was completed. Dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (B-2). The vinyl equivalent of the obtained vinyl compound (B-2) was 275 g / eq, the total chlorine was 1350 ppm, and the yield was 82%.
  • Example 5 The same operation as in Example 3 was carried out to remove the precipitated potassium chloride by filtration, which was then removed by washing with water. Since the chlorine ion in the water layer of the 6th water washing was 5 ppm or less, the water washing was completed.
  • the vinyl equivalent of the obtained vinyl compound (B-3) was 275 g / eq, the total chlorine was 2450 ppm, and the yield was 74%.
  • Comparative Example 1 The same operation was performed except that 229.0 parts of toluene was charged in place of diethylene glycol dimethyl ether in the same apparatus as in Example 1.
  • the resin precipitates and adheres to the stirrer, making stirring difficult.
  • the reaction was continued while cooling.
  • the precipitated resin was gradually dissolved, and about 3% of the residual CMS remained in the system 6 hours after the reaction.
  • the reaction time was further extended, and the residual CMS did not change even after 12 hours. Neutralization was performed and filtration was attempted, but the viscosity was high and suction filtration under reduced pressure could not be performed. Therefore, it was washed with water.
  • the liquid separation was bad and an emulsion was generated.
  • the chlorine ion in the aqueous layer that was washed with water for the sixth time was 195 ppm.
  • dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (AH1).
  • the obtained vinyl compound (A-H1) had a vinyl equivalent of 244 g / eq, total chlorine of 4360 ppm, and a yield of 68%.
  • Comparative Example 2 The same operation was performed except that a 50% potassium hydroxide aqueous solution was used instead of the solid potassium hydroxide of Comparative Example 1. Although the difficult state of stirring and the intense heat generation as in Comparative Example 1 were not observed, the residual CMS after 6 hours of the reaction remained in the system by about 3% as in Comparative Example 1, and the reaction time was extended to 12 hours. However, the amount of residual CMS did not change.
  • the obtained vinyl compound (A-H2) had a vinyl equivalent of 232 g / eq, total chlorine of 3460 ppm, and a yield of 65%.
  • Table 1 summarizes the results of Examples 1 to 5 and Comparative Examples 1 to 3.
  • the vinyl group-containing aromatic ether compound obtained in high yield by the production method of the present invention is radically polymerized in the field of electronic and electrical materials, especially circuit substrate materials that require low dielectric constant in electronic devices such as smartphones. It can be suitably used as a sex resin component.

Abstract

The present invention provides a production method by which a vinyl compound is obtained with a high yield, said vinyl compound forming a cured product that has a low dielectric loss tangent.　A method for producing a vinyl group-containing ether compound, said method being characterized in that when an ether compound having a vinyl group is produced by reacting a compound having a phenolic hydroxyl group and a vinyl aralkyl halide represented by general formula (1) with each other in a reaction solvent in the presence of an alkali metal compound, the reaction is carried out with use of a reaction solvent that contains 50% by mass or more of diethylene glycol dimethyl ether. (1): X-CH2-Ar1-CH=CH2 In the formula, Ar1 represents a benzene ring group or a naphthalene ring group; and X represents a halogen atom.

Description

ビニル基を有する芳香族エーテル化合物の製造方法Method for Producing Aromatic Ether Compound with Vinyl Group
　本発明は、フェノール性水酸基を有する化合物とビニルアラルキルハライドを反応させてなるビニル基を有する芳香族エーテル化合物の製造方法に関するものであり、反応性を改善し、副生する塩の除去を容易にし、高い収率で目的物を得られるビニル基を有する芳香族エーテル化合物の製造方法に関する。 The present invention relates to a method for producing an aromatic ether compound having a vinyl group obtained by reacting a compound having a phenolic hydroxyl group with vinyl aralkyl halide, improving the reactivity and facilitating the removal of by-products salts. The present invention relates to a method for producing an aromatic ether compound having a vinyl group, which can obtain a desired product in a high yield.
　電子・電気材料分野では、スマートフォンに代表される電子機器の急激な進化により、特に情報・通信分野では情報処理量の増大に伴い信号の高周波化が進行、伝送損失低減のために、この分野に使用される樹脂成分には低誘電率、低誘電正接が強く求められている。そこで、回路基板に代表される電子・電気材料分野では、エポキシ樹脂に変わって、より低誘電率・低誘電正接化が可能なラジカル重合性の樹脂が広く使用されるようになっている。特にビニル化合物は反応性と低誘電率、低誘電正接の特性から有望視されており、更に低誘電率、低誘電正接の特性や難燃性等の付加価値をも求められている。 In the field of electronic and electrical materials, due to the rapid evolution of electronic devices such as smartphones, the frequency of signals is increasing with the increase in the amount of information processing, especially in the field of information and communication. Low dielectric constant and low dielectric loss tangent are strongly required for the resin components used. Therefore, in the field of electronic and electrical materials represented by circuit boards, radically polymerizable resins having a lower dielectric constant and lower dielectric loss tangent are widely used instead of epoxy resins. In particular, vinyl compounds are expected to be promising because of their reactivity, low dielectric constant, and low dielectric loss tangent characteristics, and are also required to have added value such as low dielectric constant, low dielectric loss tangent characteristics, and flame retardancy.
　本発明者は、リン含有フェノール化合物や多官能フェノール樹脂等のフェノール性水酸基を有する化合物にビニル基を導入することで難燃性等を付与したビニル基を有するベンジルエーテル化合物が得られること（特許文献１）を見出している。この様なフェノール性水酸基を有する化合物とビニルアラルキルハライドの反応における反応溶媒としては、例えば、特許文献２ではＮ，Ｎジメチルホルムアミドを溶媒として提案しており、特許文献３では一価アルコール又はグリコール溶媒を、特許文献４では水に難溶なケトン系溶媒を、特許文献５ではジメチルスルホキシド、ジメチルホルムアミド、アセトニトリル、Ｎ－メチルピロリドン及び炭酸プロピレンからなる非プロトン性極性溶媒を提案している。反応させるフェノール化合物の構造により溶解性が異なる影響もあるが、溶媒種による反応性の改良は多数検討されているが、最適な溶媒は未だ見出されていなかった。 The present inventor can obtain a benzyl ether compound having a vinyl group imparted with flame retardancy by introducing a vinyl group into a compound having a phenolic hydroxyl group such as a phosphorus-containing phenol compound or a polyfunctional phenol resin (Patent). Document 1) is found. As a reaction solvent in the reaction of such a compound having a phenolic hydroxyl group and vinyl aralkyl halide, for example, Patent Document 2 proposes N, N dimethylformamide as a solvent, and Patent Document 3 proposes a monohydric alcohol or a glycol solvent. Patent Document 4 proposes a ketone solvent that is sparingly soluble in water, and Patent Document 5 proposes an aprotonic polar solvent composed of dimethylsulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, and propylene carbonate. Although the solubility may differ depending on the structure of the phenol compound to be reacted, many improvements in reactivity with solvent species have been investigated, but the optimum solvent has not yet been found.
　また、ビニル化合物の製法において、反応雰囲気についても、従来、酸素によるビニル基の阻害反応を応用して酸素又は空気雰囲気下で反応を行い、ビニル基の望ましくない重合反応を抑制する方法がとられていた。しかし、酸素雰囲気の場合、フェノール性水酸基を有する化合物の水酸基の酸化が起こり、キノン構造となることでビニルアルキルハライドとの反応性が低下する。 Further, in the method for producing a vinyl compound, conventionally, as for the reaction atmosphere, a method of suppressing an undesired polymerization reaction of vinyl groups by applying an inhibitory reaction of vinyl groups by oxygen to carry out the reaction in an oxygen or air atmosphere has been adopted. Was there. However, in the case of an oxygen atmosphere, the hydroxyl group of the compound having a phenolic hydroxyl group is oxidized, and the quinone structure reduces the reactivity with the vinyl alkyl halide.
　ビニル化合物の生成反応において副生する塩の除去についても課題があり、水洗により除去したり、塩に対して良溶媒である水等に滴下することで樹脂自体を析出して分離する方法等がとられており、水洗回数が多くなったり、析出したビニル化合物の回収、洗浄方法など作業性に課題があった。 There is also a problem in removing the salt produced as a by-product in the formation reaction of the vinyl compound, and there is a method of removing the resin by washing with water or dropping the resin into water, which is a good solvent for the salt, to precipitate and separate the resin itself. Therefore, there are problems in workability such as increasing the number of washings with water, recovering the precipitated vinyl compound, and cleaning method.
特開２００４－３３１５３７号公報Japanese Unexamined Patent Publication No. 2004-331537 特開昭６３－６８５３７号公報Japanese Unexamined Patent Publication No. 63-68537 特開平１－１５８０３４号公報Japanese Unexamined Patent Publication No. 1-158034 特開平６－１１６１９４号公報Japanese Unexamined Patent Publication No. 6-116194 国際公開第２０１９／１７６８５５号International Publication No. 2019/176855
　本発明はこれまで検討されてきたフェノール性水酸基を有する化合物とビニルアラルキルハライドを反応させてなるビニル基を有するエーテル化合物の製造方法において、好適な溶媒を見出し、反応の速度を高める手法を用い、また、効率的な塩の除去方法を見出し、従来よりも更に効率の良い製造方法を提供するものである。 The present invention uses a method for finding a suitable solvent and increasing the reaction rate in the method for producing an ether compound having a vinyl group obtained by reacting a compound having a phenolic hydroxyl group with a vinyl aralkyl halide, which has been studied so far. Further, the present invention finds an efficient salt removing method and provides a more efficient production method than the conventional one.
　すなわち、本発明は、ビニル基を有するエーテル化合物の製造方法であって、フェノール性水酸基を有する化合物と下記一般式（１）で表されるビニルアラルキルハライドとを塩基性を示すアルカリ（土類）金属化合物の存在下、反応溶媒中で反応させてビニル基を有するエーテル化合物を製造するにあたり、ジエチレングリコールジメチルエーテルを５０質量％以上含む反応溶媒を使用して反応することを特徴とするビニル基を有する芳香族エーテル化合物の製造方法である。
Figure JPOXMLDOC01-appb-C000003
  
　ここで、Ａｒ１は芳香族環基であり、Ｘはハロゲン原子である。 That is, the present invention is a method for producing an ether compound having a vinyl group, wherein a compound having a phenolic hydroxyl group and a vinyl aralkyl halide represented by the following general formula (1) are based on an alkali (earth). In producing an ether compound having a vinyl group by reacting in a reaction solvent in the presence of a metal compound, an aromatic having a vinyl group is characterized in that the reaction is carried out using a reaction solvent containing 50% by mass or more of diethylene glycol dimethyl ether. This is a method for producing a group ether compound.
Figure JPOXMLDOC01-appb-C000003
Here, Ar 1 is an aromatic ring group and X is a halogen atom.
　前記製造方法において、アルカリ（土類）金属化合物が固形のアルカリ（土類）金属水酸化物又はアルカリ（土類）金属炭酸塩であり、非水系で反応を行うことが好ましく、固形アルカリ（土類）金属化合物を分割投入することがより好ましく、不活性ガス雰囲気下で反応を行うことが好ましく、反応により生成したハロゲン化アルカリ（土類）金属をろ過により除去した後、水洗を行うことが好ましい。 In the above-mentioned production method, the alkali (earth) metal compound is a solid alkali (earth) metal hydroxide or an alkali (earth) metal carbonate, and the reaction is preferably carried out in a non-aqueous system, and the solid alkali (earth) is preferable. Kind) It is more preferable to add the metal compound in portions, it is preferable to carry out the reaction in an inert gas atmosphere, and it is possible to wash with water after removing the alkali halide (earth) metal generated by the reaction by filtration. preferable.
　前記フェノール性水酸基を有する化合物が、下記一般式（２）で表されるリン含有フェノール化合物である場合により効果的な製造方法である。
Figure JPOXMLDOC01-appb-C000004
 This is a more effective production method when the compound having a phenolic hydroxyl group is a phosphorus-containing phenol compound represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000004
　前記フェノール性水酸基を有する化合物は、フェノール性水酸基を２以上有するフェノール化合物であることが好ましい。 The compound having a phenolic hydroxyl group is preferably a phenol compound having two or more phenolic hydroxyl groups.
　また、本発明は、前記製造方法で得られたビニル基を有する芳香族エーテル化合物とラジカル開始剤とを必須成分として含有する組成物であり、それを硬化してなる硬化物である。 Further, the present invention is a composition containing an aromatic ether compound having a vinyl group obtained by the above-mentioned production method and a radical initiator as essential components, and is a cured product obtained by curing the composition.
　更には、前記製造方法で得られたビニル基含有芳香族エーテル化合物を得ること、このビニル基含有芳香族エーテル化合物にラジカル開始剤を必須成分として配合して樹脂組成物とすること、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物をラジカル重合させることを特徴とする芳香族エーテル系樹脂の製造方法、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物に繊維質基材を配合して半硬化させることを特徴とするプリプレグの製造方法、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物を樹脂フィルムに塗布し、半硬化させることを特徴とする樹脂シートの製造方法、それらプリプレグ及び／又は樹脂シートを積層して成形した積層板の製造方法である。 Further, a vinyl group-containing aromatic ether compound obtained by the above-mentioned production method can be obtained, and a radical initiator is blended with the vinyl group-containing aromatic ether compound as an essential component to prepare a resin composition. A method for producing an aromatic ether-based resin, which comprises radically polymerizing a contained aromatic ether compound or resin composition. A fibrous base material is blended with the vinyl group-containing aromatic ether compound or resin composition and semi-cured. A method for producing a prepreg, which comprises applying the vinyl group-containing aromatic ether compound or resin composition to a resin film, and a method for producing a resin sheet, which comprises semi-curing the prepreg and / or a resin thereof. This is a method for manufacturing a laminated board formed by laminating sheets.
　本発明のビニル基含有芳香族エーテル化合物の製造方法によると、フェノール性水酸基を有する化合物とビニルアラルキルハライドとを、反応溶媒としてジエチレングリコールジメチルエーテルを必須成分として反応することにより、ビニルアラルキルハライドを、効率的にフェノール性水酸基を有する化合物と反応することができ、副生する塩の除去も効率的に実施でき、高収率で目的物のビニル基含有芳香族エーテル化合物を得ることができる。 According to the method for producing a vinyl group-containing aromatic ether compound of the present invention, vinyl aralkyl halide is efficiently produced by reacting a compound having a phenolic hydroxyl group with vinyl aralkyl halide using diethylene glycol dimethyl ether as an essential component as a reaction solvent. It can react with a compound having a phenolic hydroxyl group, can efficiently remove by-produced salts, and can obtain the desired vinyl group-containing aromatic ether compound in high yield.
　以下、本発明を詳細に説明する。
　本発明のビニル基を有する芳香族エーテル化合物（以下、ビニル化合物ともいう）の製造方法は、フェノール性水酸基を有する化合物（以下、フェノール樹脂ともいう）とビニルアラルキルハライド（以下、芳香族ビニル化剤ともいう）とを、反応溶媒にジエチレングリコールジメチルエーテルを５０質量％以上使用して、反応することを特徴とする。その際、不活性ガス雰囲気下で行うことが好ましく、非水系で、固形アルカリ（土類）金属化合物を用いることが好ましい。 Hereinafter, the present invention will be described in detail.
The method for producing an aromatic ether compound having a vinyl group (hereinafter, also referred to as a vinyl compound) of the present invention comprises a compound having a phenolic hydroxyl group (hereinafter, also referred to as a phenol resin) and a vinyl aralkyl halide (hereinafter, also referred to as an aromatic vinyl agent). Also referred to as), the reaction is characterized by using 50% by mass or more of diethylene glycol dimethyl ether as the reaction solvent. At that time, it is preferable to carry out the operation in an inert gas atmosphere, and it is preferable to use a solid alkali (earth) metal compound in a non-aqueous system.
　本発明で使用できるフェノール性水酸基を有する化合物としては、特に限定はなく、公知の化合物が挙げられ、好ましくはフェノール性水酸基を２個以上有する化合物である。具体的には、ハイドロキノン、レゾルシノン、カテコール、ジブチルハイドロキノン、フロログリシノール等の単核体フェノール化合物類や、ビスフェノールＡ、ビスフェノールＦ、テトラメチルビスフェノールＦ、ビフェノール、テトラメチルビフェノール、ビスフェノールスルフォン、ビスフェノールスルフィド、ナフタレンジオール、ビスフェノールフルオレン及びそれらの異性体や置換基を持った化合物等の二核体フェノール化合物類や、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、アラルキルフェノール樹脂、アラルキルナフトール樹脂、アラルキルビスフェノール樹脂等のキシリレン構造で結合したフェノール類で構成されるフェノール樹脂、ビスメチルビフェニル構造で結合したフェノール類で構成されるフェノール樹脂類トリスヒドロキシフェニルメタン型ノボラック樹脂、ジシクロペンタジエン型フェノール樹脂及び国際公開第２０１１／０７４５１７号に記載の化合物等の多官能フェノール樹脂類や、１０－（２，５－ジヒドロキシフェニル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド、１０－（２，７－ジヒドロキシナフチル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド等の前記一般式（２）で表されるリン含有フェノール化合物類等が例示できる。これらの化合物を単独又は複数併用してもよい。 The compound having a phenolic hydroxyl group that can be used in the present invention is not particularly limited, and examples thereof include known compounds, preferably compounds having two or more phenolic hydroxyl groups. Specifically, mononuclear phenol compounds such as hydroquinone, resorcinone, catechol, dibutylhydroquinone, and fluoroglycinol, bisphenol A, bisphenol F, tetramethylbisphenol F, biphenol, tetramethylbiphenol, bisphenol sulfone, bisphenol sulfide, Dinuclear phenol compounds such as naphthalenediol, bisphenol fluorene and compounds having their isomers and substituents, phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, aralkylphenol resin, aralkylnaphthol resin, aralkylbisphenol. Phenolic resins composed of phenols bonded with a xylylene structure such as resins, phenolic resins composed of phenols bonded with a bismethylbiphenyl structure Trishydroxyphenylmethane type novolak resin, dicyclopentadiene type phenol resin and international release Polyfunctional phenolic resins such as the compounds of No. 2011/074517 and 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -(2,7-Dihydroxynaphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like can be exemplified by phosphorus-containing phenol compounds represented by the general formula (2). .. These compounds may be used alone or in combination of two or more.
　本発明で使用できるビニルアラルキルハライドは前記一般式（１）で表される。
　式（１）において、Ａｒ１は芳香族環基であり、好ましくはベンゼン環基又はナフタレン環基であり、より好ましくはベンゼン環基である。この芳香族環基は未置換であるか、置換基として、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数６～１０のアリール基、炭素数６～１０のアリールオキシ基、炭素数７～１２のアラルキル基、又は炭素数７～１２のアラルキルオキシ基を有してもよい。
　炭素数１～６のアルキル基又はアルコキシ基としては、直鎖状、分岐状、環状のいずれでもよく、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、イソプロピル基、ｓｅｃ－ブチル基、ｔ－ブチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、イソヘキシル基、シクロヘキシル基、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、イソプロポキシ基、ｓｅｃ－ブトキシ基、ｔ－ブトキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、ｔ－ペンチルオキシ基、イソヘキシルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基等が挙げられる。
　炭素数６～１０のアリール基又はアリールオキシ基としては、フェニル基、トリル基、エチルフェニル基、ｏ－キシリル基、プロピルフェニル基、メシチル基、ナフチル基、インダニル基、フェノキシ基、トリルオキシ基、エチルフェノキシ基、キシリルオキシ基、プロピルフェノキシ基、メシチルオキシ基、ナフチルオキシ基等が挙げられる。
　炭素数７～１１のアラルキル基又はアラルキルオキシ基としては、ベンジル基、メチルベンジル基、ジメチルベンジル基、トリメチルベンジル基、フェネチル基、１－フェニルエチル基、２－フェニルイソプロピル基、ナフチルメチル基、ベンジルオキシ基、メチルベンジルオキシ基、ジメチルベンジルオキシ基、トリメチルベンジルオキシ基、フェネチルオキシ基、１－フェニルエチルオキシ基、２－フェニルイソプロピルオキシ基、ナフチルメチルオキシ基等が挙げられる。 The vinyl aralkyl halide that can be used in the present invention is represented by the above general formula (1).
In the formula (1), Ar 1 is an aromatic ring group, preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. This aromatic ring group is unsubstituted or, as a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. It may have an oxy group, an arylyl group having 7 to 12 carbon atoms, or an arylyl oxy group having 7 to 12 carbon atoms.
The alkyl group or alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-pentyl group. n-hexyl group, isopropyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group , N-pentyloxy group, n-hexyloxy group, isopropoxy group, sec-butoxy group, t-butoxy group, isopentyloxy group, neopentyloxy group, t-pentyloxy group, isohexyloxy group, cyclopentyloxy Groups, cyclohexyloxy groups and the like can be mentioned.
Examples of the aryl group or aryloxy group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, an ethylphenyl group, an o-xysilyl group, a propylphenyl group, a mesityl group, a naphthyl group, an indanyl group, a phenoxy group, a tolyloxy group and an ethyl. Examples thereof include a phenoxy group, a xylyloxy group, a propylphenoxy group, a mesityloxy group, a naphthyloxy group and the like.
Examples of the aralkyl group or aralkyloxy group having 7 to 11 carbon atoms include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a phenethyl group, a 1-phenylethyl group, a 2-phenylisopropyl group, a naphthylmethyl group and a benzyl group. Examples thereof include an oxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a phenethyloxy group, a 1-phenylethyloxy group, a 2-phenylisopropyloxy group, and a naphthylmethyloxy group.
　前記ビニルアラルキルハライドとしては、クロロメチルスチレン、ブロモメチルスチレン、クロロメチルナフチレン、ブロモメチルナフチレン、及びそれらの異性体や置換基を持った化合物等が挙げられる。ビニル基の置換位置について、例えば、ビニルベンジルハライドの場合、４－位が好ましく、４－位体が全体の５０モル％以上であることがより好ましい。
　具体的には、ｐ－ビニルベンジルクロリド、ｍ－ビニルベンジルクロリド、ｐ－ビニルベンジルブロミド、ｍ－ビニルベンジルブロミド等が挙げられるが、これらに限定されるものではなく、単独で使用しても、２種類以上混合して使用してもよい。市販品としては、ＣＭＳ－１４（ＡＧＣセイミケミカル株式会社製、ｐ－ビニルベンジルクロリドとｍ－ビニルベンジルクロリドの約９５／５の混合体）、ＣＭＳ－Ｐ（ＡＧＣセイミケミカル株式会社製、ｐ－ビニルベンジルクロリドとｍ－ビニルベンジルクロリドの約５０／５０の混合物）等が挙げられる。 Examples of the vinyl aralkyl halide include chloromethylstyrene, bromomethylstyrene, chloromethylnaphthylene, bromomethylnaphthylene, and compounds having isomers and substituents thereof. Regarding the substitution position of the vinyl group, for example, in the case of vinylbenzyl halide, the 4-position is preferable, and the 4-position is more preferably 50 mol% or more of the whole.
Specific examples thereof include, but are not limited to, p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, etc., and may be used alone. Two or more types may be mixed and used. Commercially available products include CMS-14 (manufactured by AGC Seimi Chemical Co., Ltd., a mixture of about 95/5 of p-vinylbenzyl chloride and m-vinylbenzyl chloride) and CMS-P (manufactured by AGC Seimi Chemical Co., Ltd., p-). A mixture of about 50/50 of vinylbenzyl chloride and m-vinylbenzyl chloride) and the like.
　前記フェノール性水酸基を有する化合物と前記ビニルアラルキルハライドとの配合割合は、フェノール性水酸基を有する化合物中の水酸基１モルに対して、ビニルアラルキルハライドが０．８０～４．０モルが好ましく、０．９５～２．０モルがより好ましく、１．０～１．５モルが更に好ましい。フェノール性水酸基を有する化合物１モルに対して、ビニルアラルキルハライドが０．８０モル未満では残存する水酸基が多くなり、耐熱性が低下し、また、４．０モルを越えると、未反応のビニルアラルキルハライドの残存量が多くなるか、副反応の重合物が多くなりすぎる。 The compounding ratio of the compound having a phenolic hydroxyl group and the vinyl aralkyl halide is preferably 0.80 to 4.0 mol of vinyl aralkyl halide with respect to 1 mol of the hydroxyl group in the compound having a phenolic hydroxyl group. 95 to 2.0 mol is more preferable, and 1.0 to 1.5 mol is further preferable. If the amount of vinyl aralkyl halide is less than 0.80 mol, the number of residual hydroxyl groups increases and the heat resistance decreases with respect to 1 mol of the compound having a phenolic hydroxyl group, and if it exceeds 4.0 mol, unreacted vinyl aralkyl. There is too much residual halide or too much side reaction polymer.
　本発明の製造方法では、反応溶媒としてジエチレングリコールジメチルエーテルを使用する。ジエチレングリコールジメチルエーテルを反応溶媒に使用することにより、フェノール性水酸基を有する化合物とビニルアラルキルハライドとの反応が効率的に進行する。ジエチレングリコールジメチルエーテルは溶媒全体に対して、５０質量％以上であり、好ましくは８０質量％以上、より好ましくは１００質量％（単独使用）である。 In the production method of the present invention, diethylene glycol dimethyl ether is used as the reaction solvent. By using diethylene glycol dimethyl ether as the reaction solvent, the reaction between the compound having a phenolic hydroxyl group and vinyl aralkyl halide proceeds efficiently. The amount of diethylene glycol dimethyl ether is 50% by mass or more, preferably 80% by mass or more, and more preferably 100% by mass (single use) with respect to the total solvent.
　また併用できる溶媒としては、特に限定はないが、非水系溶媒が好ましい。例えば、ヘキサン、へプタン、オクタン、デカン、ジメチルブタン、ペンテン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン等の炭化水素類や、プロパノール、ブタノール、アミルアルコール、ペンタノール、ヘキサノール、メチルアミルアルコール、ヘプタノール、シクロヘキサノール、ベンジルアルコール、フリフリルアルコール等のアルコール類や、エチルエーテル、イソプロピルエーテル、ブチルエーテル、ジイソアミルエーテル、メチルフェニルエーテル、エチルフェニルエーテル、アミルフェニルエーテル、エチルベンジルエーテル、ジオキサン、メチルフラン、テトラヒドロフラン等のエーテル類や、アセトン、メチルアセトン、メチルエチルケトン、メチルプロピルケトン、メチルブチルケトン、メチルアミルケトン、ジエチルケトン、エチルブチルケトン、ジプロピルケトン、シクロヘキサノン等のケトン類や、メチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブ、セロソルブアセテート、エチレングリコールイソプロピルエーテル、メチルエチルカルビトール、プロピレングリコールモノメチルエーテル、ジメチルホルムアミド、ジメチルスルホキシド等が挙げられるが、これらに限定されるものではない。また、反応で生成した塩を水洗により除去する場合は水層を分液可能な溶媒を使用することが好ましい。例えば、ベンゼン、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。 The solvent that can be used in combination is not particularly limited, but a non-aqueous solvent is preferable. For example, hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, penten, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, propanol, butanol, amyl alcohol, pentanol, hexanol, methyl amyl alcohol. , Heptanol, cyclohexanol, benzyl alcohol, frifryl alcohol and other alcohols, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methylphenyl ether, ethylphenyl ether, amylphenyl ether, ethylbenzyl ether, dioxane, methylfuran , Ethers such as tetrahydrofuran, acetone, methyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, cyclohexanone and other ketones, methyl cellosolve, methyl cellosolve. Examples thereof include, but are not limited to, acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, and dimethyl sulfoxide. When the salt produced by the reaction is removed by washing with water, it is preferable to use a solvent capable of separating the aqueous layer. For example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and the like can be mentioned.
　本発明の製造方法は、不活性ガス雰囲気下で反応させることが好ましい。活性ガスとは、窒素、アルゴン等が挙げられる。ビニル化合物の合成ではビニル基の重合反応を抑えるため、しばしば酸素を用いる場合があるが、フェノール基の酸化が起きてしまい、ビニルアラルキルハライドとの反応性が低下する場合がある。そのため、不活性ガス雰囲気下で反応することが好ましい。 The production method of the present invention preferably reacts in an atmosphere of an inert gas. Examples of the active gas include nitrogen and argon. Oxygen is often used in the synthesis of vinyl compounds in order to suppress the polymerization reaction of vinyl groups, but the oxidation of phenol groups may occur and the reactivity with vinyl aralkyl halide may decrease. Therefore, it is preferable to react in an inert gas atmosphere.
　本発明の製造方法は、塩基性を示すアルカリ金属化合物又はアルカリ土類金属化合物の存在下で反応を行う。本明細書において、アルカリ（土類）金属は、アルカリ金属又はアルカリ土類金属又は両者を意味する。
　固形の塩基性のアルカリ（土類）金属化合物を用いて反応することが好ましい。固形アルカリ（土類）金属化合物は、原料ビニルアラルキルハライドのハロゲンと反応し、リン含有フェノール樹脂などのフェノール性水酸基を有する化合物との反応を促進させるものである。例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物や、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩や、水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属の水酸化物等のアルカリ性の化合物が挙げられ、反応の促進効果という点から、アルカリ（土類）金属の水酸化物又はアルカリ金属の炭酸塩が好ましい。また、単独で使用しても、２種類以上併用してもよい。非水系で反応を行うことが収率向上の面で好ましいので、固形で使用することが好ましい。
　アルカリ（土類）金属化合物の使用量は、水酸化アルカリ金属の場合はビニルアラルキルハライド１モルに対して、０．５～５．０モルであり、１～３モルが好ましく、１．２～２モルがより好ましい。この使用量が０．５モル未満の場合、反応が十分行われない。一方、５．０モルを越えると、中和に必要な酸が多量に必要となるため経済的に好ましくない。なお、水酸化アルカリ土類金属や炭酸アルカリ金属場合は、上記の１／２倍モルが適する。 In the production method of the present invention, the reaction is carried out in the presence of an alkali metal compound or an alkaline earth metal compound showing basicity. As used herein, the alkaline (earth) metal means an alkali metal, an alkaline earth metal, or both.
It is preferable to react with a solid basic alkaline (earth) metal compound. The solid alkali (earth) metal compound reacts with the halogen of the raw material vinyl aralkyl halide to promote the reaction with a compound having a phenolic hydroxyl group such as a phosphorus-containing phenol resin. For example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide. Alkaline compounds such as hydroxides of the above can be mentioned, and alkali (earth) metal hydroxides or alkali metal carbonates are preferable from the viewpoint of promoting the reaction. Further, it may be used alone or in combination of two or more. Since it is preferable to carry out the reaction in a non-aqueous system from the viewpoint of improving the yield, it is preferable to use it as a solid.
The amount of the alkaline (earth) metal compound used is 0.5 to 5.0 mol, preferably 1 to 3 mol, and 1.2 to 3 mol, relative to 1 mol of vinyl aralkyl halide in the case of alkali metal hydroxide. 2 mol is more preferred. If this amount is less than 0.5 mol, the reaction will not be sufficient. On the other hand, if it exceeds 5.0 mol, a large amount of acid required for neutralization is required, which is economically unfavorable. In the case of alkaline earth metal hydroxide or alkali metal carbonate, 1/2 times the above mole is suitable.
　そして、系内のｐＨを確認しながらｐＨが高くならないように分割投入し、反応で消費したのちに追加投入することが望ましい。系内のｐＨは系内サンプルに水を添加し、ｐＨ試験紙で確認することができる。ｐＨ１０以下、より好ましくはｐＨ９以下を保持するように分割数、添加タイミングを調整することが望ましい。
　ｐＨ１１以上での反応を行うと、フェノール性水酸基として、リン含有フェノール化合物を使用するような場合、一部のリン含有フェノール化合物は分解反応が起きてしまい、所望の化合物が得られず、収率の悪化につながってしまう。さらに、系内に水分を含んで反応した場合は、前記分解反応が加速してしまうことから非水系で反応することが好ましい。また、非水系で反応を行うことで反応溶媒のジエチレングリコールジメチルエーテルを容易にリサイクルすることができるので経済的にも有利である。 Then, while checking the pH in the system, it is desirable to separately add the pH so that the pH does not increase, and after consuming in the reaction, add the pH. The pH in the system can be confirmed by adding water to the sample in the system and using pH test paper. It is desirable to adjust the number of divisions and the timing of addition so as to maintain pH 10 or less, more preferably pH 9 or less.
When the reaction is carried out at pH 11 or higher, when a phosphorus-containing phenol compound is used as the phenolic hydroxyl group, some phosphorus-containing phenol compounds undergo a decomposition reaction, and a desired compound cannot be obtained, resulting in a yield. Will lead to deterioration of. Further, when the reaction contains water in the system, the decomposition reaction is accelerated, so that it is preferable to react in a non-aqueous system. Further, by carrying out the reaction in a non-aqueous system, the reaction solvent diethylene glycol dimethyl ether can be easily recycled, which is economically advantageous.
　反応温度は、３０～１５０℃が好ましく、４０～１００℃がより好ましく、５０～９０℃が更に好ましい。反応温度が高いとビニル基の反応により重合してしまい、低すぎると反応が進まず効率が悪い。
　反応の追跡には、ｐＨによるアルカリ金属化合物の消費の追跡や、各種クロマトグラフィーやＩＲ、ＵＶ等によりビニルアラルキルハライドの残存量の追跡等により確認することができる。例えば、原料のビニルアラルキルハライドの残存量や、反応に関わる官能基のピークを測定することで終点を決定することができる。 The reaction temperature is preferably 30 to 150 ° C, more preferably 40 to 100 ° C, still more preferably 50 to 90 ° C. If the reaction temperature is high, polymerization will occur due to the reaction of vinyl groups, and if it is too low, the reaction will not proceed and the efficiency will be poor.
The reaction can be confirmed by tracking the consumption of the alkali metal compound by pH, tracking the residual amount of vinyl aralkyl halide by various chromatographies, IR, UV, or the like. For example, the end point can be determined by measuring the residual amount of vinyl aralkyl halide as a raw material and the peak of the functional group involved in the reaction.
　また、反応は重合禁止剤の存在下で行ってもよい。重合禁止剤を添加することにより、反応に供するビニルアラルキルハライド、又は目的生成物であるビニル基含有芳香族エーテル化合物が重合してオリゴマーを副生することを防止することができる。重合禁止剤には公知のものを制限なく用いることができ、ヒドロキノン、ヒドロキシモノメチルエーテル、ｔ－ブチルカテコール、ｔ－ブチルハイドロキノン、４－メトキシフェノール、４－メトキシ－１－ナフトール、フェノチアジン等の有機化合物の他、塩化銅、硫化銅等の銅化合物等が挙げられ、これらを組み合わせて使用してもよい。 Further, the reaction may be carried out in the presence of a polymerization inhibitor. By adding a polymerization inhibitor, it is possible to prevent the vinyl aralkyl halide used in the reaction or the vinyl group-containing aromatic ether compound which is the target product from polymerizing to form an oligomer as a by-product. Known polymerization inhibitors can be used without limitation, and organic compounds such as hydroquinone, hydroxymonomethyl ether, t-butylcatechol, t-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine can be used. In addition, copper compounds such as copper chloride and copper sulfide may be mentioned, and these may be used in combination.
　本発明の製法によれば、好ましくは反応時間１０時間以内、より好ましくは７時間以内で、原料ビニルアラルキルハライドを残存させることなく、反応を完結することができる。副生物のアルカリ（土類）金属ハロゲン化物についても、濾過、水洗によって簡便に除去でき、水洗における水層の塩素イオンを好ましくは１００ｐｐｍ以下、より好ましくは３０ｐｐｍ以下に低減可能である。こうして得られるビニル化合物の収率は、好ましくは７０％以上、より好ましくは８０％以上、さらに好ましくは９０％以上である。 According to the production method of the present invention, the reaction can be completed within 10 hours, more preferably within 7 hours, without leaving the raw material vinyl aralkyl halide. Alkaline (earth) metal halides as by-products can also be easily removed by filtration and washing with water, and the chlorine ions in the aqueous layer in washing with water can be reduced to preferably 100 ppm or less, more preferably 30 ppm or less. The yield of the vinyl compound thus obtained is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.
　この反応の終了後、得られた反応液（反応混合物）を必要により、反応溶媒の留去、溶媒置換等を実施し、水等による洗浄や、活性炭処理、シリカゲルクロマトグラフィー等の手段を利用して精製し、目的のビニル基含有芳香族エーテル化合物を取り出すことができる。 After completion of this reaction, the obtained reaction solution (reaction mixture) is subjected to distillation of the reaction solvent, solvent substitution, etc., if necessary, and washing with water or the like, activated charcoal treatment, silica gel chromatography, or the like is used. The desired vinyl group-containing aromatic ether compound can be extracted by purification.
　本発明の製法によって得られるビニル基含有芳香族エーテル化合物は、ビニル当量が１００～５００ｇ／ｅｑ．が好ましく、より好ましくは２００～３００ｇ／ｅｑ．であり、全塩素量が好ましくは３０００ｐｐｍ以下、より好ましくは２０００ｐｐｍ以下である。 The vinyl group-containing aromatic ether compound obtained by the production method of the present invention has a vinyl equivalent of 100 to 500 g / eq. Is preferable, and more preferably 200 to 300 g / eq. The total amount of chlorine is preferably 3000 ppm or less, more preferably 2000 ppm or less.
　フェノール性水酸基を有する化合物として好適なリン含有フェノール樹脂は前記一般式（２）で表される。
　一般式（２）において、Ｒ１及びＲ２はそれぞれ独立に炭素数１～１５の酸素原子を有してもよい炭化水素基であり、直鎖状、分岐状、環状のいずれでもよく、芳香族環構造を有する基が好ましく、Ｒ１とＲ２で環状構造を形成していてもよい。
　炭素数１～１５の酸素原子を有してもよい炭化水素基としては、例えば、炭素数１～１５の直鎖、分岐鎖、又は環状のアルキル基、炭素数１～１５の直鎖、分岐鎖、又は環状又はアルコキシ基、炭素数６～１５のアリール基、炭素数６～１５のアリールオキシ基、炭素数７～１５のアラルキル基、又は炭素数７～１５のアラルキルオキシ基等が挙げられる。具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、シクロペンチル基、ｎ－ヘキシル基、イソヘキシル基、シクロヘキシル基、ｎ－ヘプチル基、シクロヘプチル基、メチルシクロヘキシル基、ｎ－オクチル基、シクロオクチル基、ｎ－ノニル基、３，３，５－トリメチルシクロヘキシル基、ｎ－デシル基、シクロデシル基、ｎ－ウンデシル基、ｎ－ドデシル基、シクロドデシル基、ベンジル基、メチルベンジル基、ジメチルベンジル基、トリメチルベンジル基、ナフチルメチル基、フェネチル基、２－フェニルイソプロピル基等が挙げられる。
　また、Ｒ１及びＲ２が芳香族環構造を有する場合、その芳香族環には炭素数１～９の置換基を有していてもよい。炭素数１～９の置換基としては、例えば、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数６～９のアリール基、炭素数６～９のアリールオキシ基、炭素数７～９のアラルキル基、又は炭素数７～９のアラルキルオキシ基が挙げられる。具体的には、前記に例示した置換基が挙げられ、メチル基、シクロヘキシル基、フェニル基、トリル基、ベンジル基が好ましく、メチル基、フェニル基、ベンジル基がより好ましい。
　なお、酸素原子は炭化水素鎖又は炭化水素環を構成する炭素間に含まれることができる。 A phosphorus-containing phenolic resin suitable as a compound having a phenolic hydroxyl group is represented by the above general formula (2).
In the general formula (2), R 1 and R 2 are hydrocarbon groups that may independently have oxygen atoms having 1 to 15 carbon atoms, and may be linear, branched, or cyclic, and have an aromatic fragrance. A group having a group ring structure is preferable, and R 1 and R 2 may form a cyclic structure.
Hydrocarbon groups that may have an oxygen atom having 1 to 15 carbon atoms include, for example, a linear or branched alkyl group having 1 to 15 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms, or a branched hydrocarbon group. Examples thereof include a chain or a cyclic or alkoxy group, an aryl group having 6 to 15 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aralkyloxy group having 7 to 15 carbon atoms, and the like. .. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, Cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group , N-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group And so on.
When R 1 and R 2 have an aromatic ring structure, the aromatic ring may have a substituent having 1 to 9 carbon atoms. Examples of the substituent having 1 to 9 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, and an aryloxy group having 6 to 9 carbon atoms. Examples thereof include an arylyl group having 7 to 9 carbon atoms and an aralkylyloxy group having 7 to 9 carbon atoms. Specific examples thereof include the substituents exemplified above, preferably a methyl group, a cyclohexyl group, a phenyl group, a trill group and a benzyl group, and more preferably a methyl group, a phenyl group and a benzyl group.
The oxygen atom can be contained between the carbons constituting the hydrocarbon chain or the hydrocarbon ring.
　前記Ａｒ２は芳香族環基であり、原料キノン化合物に由来する構造である。芳香族環基は、ベンゼン環基、ナフタレン環基、ビフェニル環基、ターフェニル環基等が挙げられ、好ましくはベンゼン環基又はナフタレン環基である。この芳香族環基は未置換であるか、前記Ａｒ１で例示した置換基を有してもよい。 The Ar 2 is an aromatic ring group and has a structure derived from the raw material quinone compound. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a biphenyl ring group, a terphenyl ring group and the like, and a benzene ring group or a naphthalene ring group is preferable. This aromatic ring group may be unsubstituted or may have a substituent exemplified by Ar 1 above.
　リン含有フェノール樹脂としては、例えば、１０－（２，５－ジヒドロキシフェニル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド（例えば、ＨＣＡ－ＨＱ、三光化学株式会社製）、１０－（２，７－ジヒドロキシナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド（例えば、ＨＣＡ―ＮＱ、三光化学株式会社製）、１０－（２，５－ジヒドロキシフェニル）－８－ベンジル－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド、１０－［２－（ジヒドロキシナフチル）］－８－ベンジル－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド、ジフェニルホスフィニルヒドロキノン、ジフェニルホスフィニル－１，４－ジオキシナフタリン、１，４－シクロオクチレンホスフィニル－１，４－フェニルジオール、１，５－シクロオクチレンホスフィニル－１，４－フェニルジオール等が挙げられるが、これらに限定されるものではない。これらのリン含有フェノール樹脂は単独で使用しても、２種類以上混合して使用してもよい。 Examples of the phosphorus-containing phenol resin include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (for example, HCA-HQ, manufactured by Sanko Chemical Co., Ltd.), 10 -(2,7-Dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (eg, HCA-NQ, manufactured by Sanko Kagaku Co., Ltd.), 10- (2,5-dihydroxyphenyl)- 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- [2- (dihydroxynaphthyl)]-8-benzyl-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, 1,5- Examples thereof include, but are not limited to, cyclooctylenephosphinyl-1,4-phenyldiol. These phosphorus-containing phenolic resins may be used alone or in combination of two or more.
　反応には、必要に応じて、触媒を使用することもできる。使用する触媒としては、例えば、ベンジルジメチルアミン等の第３級アミン類や、テトラメチルアンモニウムクロリド、テトラメチルアンモニウムブロミド、テトラブチルアンモニウムブロミド等の第４級アンモニウム塩類や、トリフェニルホスフィン、トリス（２，６－ジメトキシフェニル）ホスフィン等のホスフィン類や、ベンジルトリフェニルホスホニウムクロリド、テトラブチルホスホニウムブロミド、エチルトリフェニルホスホニウムブロミド、テトラブチルホスホニウムイオダイド等のホスホニウム塩類や、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール等のイミダゾール類等の各種触媒が挙げられるが、これらに限定されるものではなく、単独で使用しても、２種類以上併用してもよい。触媒の使用量は、原料１００質量部に対して、１０質量部以下である。 A catalyst can be used for the reaction if necessary. Examples of the catalyst used include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide, triphenylphosphine, and tris (2). , 6-Dimethoxyphenyl) phosphines such as phosphine, phosphonium salts such as benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutylphosphonium iodide, 2-methylimidazole, 2-ethyl- Examples thereof include various catalysts such as imidazoles such as 4-methylimidazole, but the present invention is not limited to these, and they may be used alone or in combination of two or more. The amount of the catalyst used is 10 parts by mass or less with respect to 100 parts by mass of the raw material.
　本発明の製法によって得られたビニル基含有芳香族エーテル化合物は、樹脂又は樹脂硬化物にすることができる。
　本発明の樹脂組成物は、ビニル基含有芳香族エーテルとラジカル開始剤を必須成分として含む。この樹脂組成物は、樹脂を含んでも、含まなくてもよく、含まない場合は樹脂前駆体となる。 The vinyl group-containing aromatic ether compound obtained by the production method of the present invention can be made into a resin or a cured resin product.
The resin composition of the present invention contains a vinyl group-containing aromatic ether and a radical initiator as essential components. This resin composition may or may not contain a resin, and if it does not contain the resin, it becomes a resin precursor.
　本発明の樹脂組成物には、ラジカル開始剤を配合する。ラジカル開始剤としては、例えば、メチルエチルケトンパーオキシド、シクロヘキサノンパーオキシド、メチルアセテートパーオキシド、アセチルアセトンパーオキシド、クメンハイドロパーオキシド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン－３、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルクミルパーオキサイド、α，α’－ビス（ｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキシイソフタレート、ｔ－ブチルパーオキシベンゾエート、２，２－ビス（ｔ－ブチルパーオキシ）ブタン、２，２－ビス（ｔ－ブチルパーオキシ）オクタン、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ジ（トリメチルシリル）パーオキサイド、トリメチルシリルトリフェニルシリルパーオキサイド等の過酸化物があるがこれらに限定されない。また過酸化物ではないが、２，３－ジメチル－２，３－ジフェニルブタンも、ラジカル開始剤として使用できる。しかし、これらの例に限定されるものではなく、ラジカル開始剤２種以上を組み合わせて用いてもよい。 A radical initiator is blended in the resin composition of the present invention. Examples of the radical initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetate peroxide, acetyl acetone peroxide, cumene hydroperoxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-. Dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t) -Butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylper Oxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di There are peroxides such as (trimethylsilyl) peroxide and trimethylsilyltriphenylsilyl peroxide, but the present invention is not limited thereto. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the present invention is not limited to these examples, and two or more radical initiators may be used in combination.
　本発明の樹脂組成物には、各種硬化性樹脂や熱可塑性樹脂又は他の重合性化合物を配合することができる。 The resin composition of the present invention can be blended with various curable resins, thermoplastic resins or other polymerizable compounds.
　硬化性樹脂又は硬化性樹脂を与える他の重合性化合物としては、例えば、不飽和ポリエステル樹脂、硬化型マレイミド樹脂、ポリシアナート樹脂、フェノール樹脂、分子中に１個以上の重合性不飽和炭化水素基を有する１種以上のビニル化合物類等を挙げることができる。低誘電率、低誘電正接の観点から好ましくは、分子中に１個以上の重合性不飽和炭化水素基を有する１種以上のビニル化合物類である。 Examples of the curable resin or other polymerizable compound that gives the curable resin include unsaturated polyester resin, curable maleimide resin, polycyanate resin, phenol resin, and one or more polymerizable unsaturated hydrocarbon groups in the molecule. One or more vinyl compounds having one or more can be mentioned. 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.
　分子中に１個以上の重合性不飽和炭化水素基を有する１種以上のビニル化合物類（以下、ビニル化合物類ともいう。）である場合、その種類は特に限定されない。すなわち、ビニル化合物類は、本発明のビニル化合物と反応させることによって、架橋を形成させて、硬化させることができるものであればよい。重合性不飽和炭化水素基が炭素－炭素不飽和二重結合であるものがより好ましく、炭素－炭素不飽和二重結合を分子中に２個以上有する化合物がより好ましい。 When it is one or more vinyl compounds (hereinafter, also referred to as vinyl compounds) having one or more polymerizable unsaturated hydrocarbon groups in the molecule, the type is not particularly limited. That is, the vinyl compounds may be any one that can be cured by forming a crosslink by reacting with the vinyl compound of the present invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.
　このようなビニル化合物類の１分子当たりの炭素－炭素不飽和二重結合の平均個数（重合性二重結合数ともいう。）は、ビニル化合物類のＭｗによって異なるが、例えば、１～２０個であることが好ましく、２～１８個であることがより好ましい。この重合性二重結合数が少なすぎると、硬化物の耐熱性としては充分なものが得られにくい傾向がある。また、これが多すぎると、反応性が高くなりすぎ、例えば、組成物の保存安定性が低下したり、組成物の流動性が低下したりする等の不具合が発生するおそれがある。 The average number of carbon-carbon unsaturated double bonds per molecule of such vinyl compounds (also referred to as the number of polymerizable double bonds) varies depending on the Mw of the vinyl compounds, but is, for example, 1 to 20. It is preferable that the number is 2, and the number is more preferably 2 to 18. If the number of the polymerizable double bonds is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. On the other hand, if this amount is too large, the reactivity becomes too high, and there is a possibility that problems such as a decrease in storage stability of the composition and a decrease in the fluidity of the composition may occur.
　前記ビニル化合物類としては、トリアリルイソシアヌレート（ＴＡＩＣ）等のトリアルケニルイソシアヌレート化合物、末端が（メタ）アクリロイル基やスチリル基で変性された変性ポリフェニレンエーテル（ＰＰＥ）、分子中に（メタ）アクリロイル基を２個以上有する多官能（メタ）アクリレート化合物、ポリブタジエン等のように分子中にビニル基を２個以上有するビニル化合物類（多官能ビニル化合物類）、及びスチレン、ジビニルベンゼン等のビニルベンジル化合物等が挙げられる。この中でも、炭素－炭素二重結合を分子中に２個以上有するものが好ましく、具体的には、ＴＡＩＣ、多官能（メタ）アクリレート化合物、変性ＰＰＥ樹脂、多官能ビニル化合物類、及びジビニルベンゼン化合物等が挙げられる。これらを用いると、硬化反応により架橋がより好適に形成されると考えられ、樹脂組成物の硬化物の耐熱性をより高めることができる。また、これらを単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、炭素－炭素不飽和二重結合を分子中に１個有する化合物を併用してもよい。炭素－炭素不飽和二重結合を分子中に１個有する化合物としては、分子中にビニル基を１個有する化合物（モノビニル化合物類）等が挙げられる。 Examples of the vinyl compounds include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ether (PPE) having a terminal modified with a (meth) acryloyl group or a styryl group, and (meth) acryloyl in the molecule. Polyfunctional (meth) acrylate compounds having two or more groups, vinyl compounds having two or more vinyl groups in the molecule (polyfunctional vinyl compounds) such as polybutadiene, and vinyl benzyl compounds such as styrene and divinylbenzene. And so on. Among these, those having two or more carbon-carbon double bonds in the molecule are preferable, and specifically, TAIC, a polyfunctional (meth) acrylate compound, a modified PPE resin, a polyfunctional vinyl compound, and a divinylbenzene compound. And so on. When these are used, it is considered that cross-linking is more preferably formed by the curing reaction, and the heat resistance of the cured product of the resin composition can be further enhanced. Further, these may be used alone or in combination of two or more. Further, a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination. Examples of the compound having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
　熱可塑性樹脂としては、例えば、ポリスチレン、ポリフェニレンエーテル樹脂、ポリエーテルイミド樹脂、ポリエーテルサルホン樹脂、ＰＰＳ樹脂、ポリシクロペンタジエン樹脂、ポリシクロオレフィン樹脂等や、既知の熱可塑性エラストマー（例えば、スチレン－エチレン－プロピレン共重合体、スチレン－エチレン－ブチレン共重合体、スチレン－ブタジエン共重合体、スチレン－イソプレン共重合体、水添スチレン－ブタジエン共重合体、水添スチレン－イソプレン共重合体等）や、ゴム類（例えばポリブタジエン、ポリイソプレン）等を挙げることができる。ポリフェニレンエーテル樹脂（未変性）、水添スチレン－ブタジエン共重合体等が好ましい。 Examples of the thermoplastic resin include polystyrene, polyphenylene ether resin, polyetherimide resin, polyether sulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin and the like, and known thermoplastic elastomers (for example, styrene-). Ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.) and , Rubbers (eg, polybutadiene, polyisoprene) and the like. Polyphenylene ether resin (unmodified), hydrogenated styrene-butadiene copolymer and the like are preferable.
　本発明の樹脂組成物には、充填剤を配合することができる。充填剤としては、樹脂組成物の硬化物の耐熱性や難燃性を高めるために添加するもの等が挙げられ、公知の充填剤を使用することができるが、特に限定されない。また、充填剤を含有させることによって、耐熱性、寸法安定性や難燃性等を更に高めることができる。具体的には、球状シリカ等のシリカ、アルミナ、酸化チタン、及びマイカ等の金属酸化物、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物、タルク、焼成タルク、クレー、カオリン、酸化チタン、ガラス粉末、シリカバルーン、ホウ酸アルミニウム、硫酸バリウム、及び炭酸カルシウム等や、ガラス繊維、パルプ繊維、合成繊維、セラミック繊維等が挙げられるがこれらに限定されるものではなく、単独で使用しても、２種類以上併用してもよい。更に顔料等を配合してもよい。水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物を用いた場合、難燃助剤として作用し、リン含有率が少なくても難燃性を確保することができる。この中でも、シリカ、マイカ、及びタルクが好ましく、球状シリカがより好ましい。また、これらの１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 A filler can be added to the resin composition of the present invention. Examples of the filler include those added to enhance the heat resistance and flame retardancy of the cured product of the resin composition, and known fillers can be used, but the filler is not particularly limited. Further, by containing a filler, heat resistance, dimensional stability, flame retardancy and the like can be further improved. Specifically, silica such as spherical silica, alumina, titanium oxide, metal oxides such as mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, etc. Examples thereof include glass powder, silica balloon, aluminum borate, barium sulfate, calcium carbonate, etc., glass fiber, pulp fiber, synthetic fiber, ceramic fiber, etc., but are not limited thereto, and may be used alone. Two or more types may be used in combination. Further, a pigment or the like may be blended. When a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retardant aid, and flame retardancy can be ensured even if the phosphorus content is low. Among these, silica, mica, and talc are preferable, and spherical silica is more preferable. Further, one of these may be used alone, or two or more thereof may be used in combination.
　充填剤は、そのまま用いてもよいが、エポキシシランタイプ又はアミノシランタイプ等のシランカップリング剤で表面処理したものを用いてもよい。このシランカップリング剤としては、ラジカル開始剤との反応性との観点から、ビニルシランタイプ、メタクリロキシシランタイプ、アクリロキシシランタイプ、及びスチリルシランタイプのシランカップリング剤が好ましい。これにより、金属箔との接着強度や樹脂同士の層間接着強度が高まる。また、充填剤に予め表面処理する方法でなく、前記シランカップリング剤をインテグラルブレンド法で添加して用いてもよい。 The filler may be used as it is, or may be surface-treated with a silane coupling agent such as an epoxy silane type or an amino silane type. As the silane coupling agent, a vinylsilane type, a methacrylate silane type, an acryloxysilane type, and a styrylsilane type silane coupling agent are preferable from the viewpoint of reactivity with a radical initiator. As a result, the adhesive strength with the metal foil and the interlayer adhesive strength between the resins are increased. Further, instead of the method of surface-treating the filler in advance, the silane coupling agent may be added and used by the integral blend method.
　充填剤の含有量は、充填剤を除く固形分（モノマー等の有機成分と難燃剤を含み、溶剤を除く。）の合計１００質量部に対して、１０～２００質量部であることが好ましく、３０～１５０質量部であることが好ましい。 The content of the filler is preferably 10 to 200 parts by mass with respect to a total of 100 parts by mass of the solid content excluding the filler (including organic components such as monomers and flame retardants and excluding the solvent). It is preferably 30 to 150 parts by mass.
　本発明の樹脂組成物には、前記以外の添加剤を更に含有してもよい。添加剤としては、例えば、シリコーン系消泡剤及びアクリル酸エステル系消泡剤等の消泡剤、熱安定剤、帯電防止剤、紫外線吸収剤、染料や顔料、滑剤、湿潤分散剤等の分散剤等が挙げられる。 The resin composition of the present invention may further contain additives other than the above. Examples of the additive include dispersion of defoaming agents such as silicone-based defoaming agents and acrylic acid ester-based defoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and wet dispersants. Agents and the like can be mentioned.
　本発明の樹脂組成物を重合、硬化又は成形させて得られる成形物ないし硬化物（本明細書では、架橋反応を伴わない熱可塑性樹脂様のものも含む）は、各種用途の成型物、積層物、注型物、接着剤、塗膜、フィルムとして使用できる。例えば、半導体封止材料の硬化物は注型物又は成型物であり、かかる用途の硬化物を得る方法としては、樹脂組成物を注型、或いはトランスファー成形機、射出成形機等を用いて成形し、更に８０～２３０℃で０．５～１０時間加熱することにより硬化物を得ることができる。 Molded products or cured products obtained by polymerizing, curing or molding the resin composition of the present invention (including thermoplastic resin-like products not accompanied by a crosslinking reaction in the present specification) are molded products and laminated products for various purposes. It can be used as an object, a cast object, an adhesive, a coating film, and a film. For example, the cured product of the semiconductor encapsulation material is a cast product or a molded product, and as a method for obtaining a cured product for such an application, the resin composition is cast or molded using a transfer molding machine, an injection molding machine, or the like. Further, the cured product can be obtained by further heating at 80 to 230 ° C. for 0.5 to 10 hours.
　本発明の樹脂組成物は、プリプレグとして使用することもできる。プリプレグを製造する際には、プリプレグを形成するための基材（繊維質基材）に含浸する目的、あるいは回路基板を形成する回路基板材料とする目的でワニス状に調製して、樹脂ワニスとすることができる。この樹脂ワニスは、回路基板用に適し、回路基板材料用ワニスとして使用できる。なお、ここでいう回路基板材料の用途は、具体的には、プリント配線基板、プリント回路板、フレキシブルプリント配線板、ビルドアップ配線板等が挙げられる。 The resin composition of the present invention can also be used as a prepreg. When manufacturing a prepreg, it is prepared in the form of a varnish for the purpose of impregnating the base material (fibrous base material) for forming the prepreg or for the purpose of using it as a circuit board material for forming a circuit board, and using a resin varnish. can do. This resin varnish is suitable for circuit boards and can be used as a varnish for circuit board materials. Specific examples of the use of the circuit board material referred to here include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.
　前記の樹脂ワニスに用いられる有機溶媒としては、硬化反応を阻害しないものであれば、特に限定されない。例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類；ジメチルアセトアミド、ジメチルホルムアミド等の極性溶剤類；トルエン、キシレン等の芳香族炭化水素溶剤類等が挙げられ、これらを１種又は２種以上を混合して使用することも可能である。誘電特性の観点から、ベンゼン、トルエン、キシレン等の芳香族炭化水素類が好ましい。 The organic solvent used for the resin varnish is not particularly limited as long as it does not inhibit the curing reaction. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; polar solvents such as dimethylacetamide and dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene. It is also possible to use one kind or a mixture of two or more kinds of these. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.
　樹脂ワニスを作成する際に、使用する有機溶剤の量は、本発明の樹脂組成物１００重量％に対して、好ましくは５～９００重量％、より好ましくは１０～７００重量％、特に好ましくは２０～５００重量％である。 The amount of the organic solvent used in preparing the resin varnish is preferably 5 to 900% by weight, more preferably 10 to 700% by weight, and particularly preferably 20 with respect to 100% by weight of the resin composition of the present invention. ~ 500% by weight.
　プリプレグを作成するのに用いられる基材としては、公知の材料が用いられる。例えば、ガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙等の基材がそれぞれ単独で、又は２種以上併せて用いられる。これら基材には、必要に応じて、樹脂と基材の界面における接着性を改善する目的でカップリング剤を用いることができる。カップリング剤としては、シランカップリング剤、チタネートカップリング剤、アルミニウム系カップリング剤、ジルコアルミネートカップリング剤等一般のものが使用できる。 A known material is used as the base material used to prepare the prepreg. For example, base materials such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper are used individually or in combination of two or more. If necessary, a coupling agent can be used for these base materials for the purpose of improving the adhesiveness at the interface between the resin and the base material. As the coupling agent, general agents such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used.
　プリプレグを得る方法としては、前記樹脂ワニスを基材に含浸させた後、乾燥する方法が挙げられる。含浸は浸漬（ディッピング）、塗布等によって行われる。含浸は必要に応じて複数回繰り返すことも可能であり、またこの際、組成や濃度の異なる複数の溶液を用いて含浸を繰り返し、最終的に希望とする樹脂組成及び樹脂量に調整することも可能である。含浸後に、１００～１８０℃で１～３０分加熱乾燥することでプリプレグを得ることができる。ここで、プリプレグ中の樹脂量は、樹脂分３０～８０重量％とすることが好ましい。 Examples of the method for obtaining the prepreg include a method in which the base material is impregnated with the resin varnish and then dried. Impregnation is performed by dipping, coating, or the like. The impregnation can be repeated multiple times as needed, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust to the desired resin composition and amount. It is possible. After impregnation, a prepreg can be obtained by heating and drying at 100 to 180 ° C. for 1 to 30 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by weight of the resin content.
　本発明の組成物は、積層板としても使用することもできる。プリプレグを用いて積層板を形成する場合は、プリプレグを一枚又は複数枚積層し、片側又は両側に金属箔を配置して積層物を構成し、この積層物を加熱・加圧して積層一体化する。ここで金属箔としては、銅、アルミニウム、真鍮、ニッケル等の単独、合金、複合の金属箔を用いることができる。積層物を加熱加圧する条件としては、樹脂組成物が硬化する条件で適宜調整して加熱加圧すればよいが、加圧の圧力があまり低いと、得られる積層板の内部に気泡が残留し、電気的特性が低下する場合があるため、成形性を満足する条件で加圧することが好ましい。例えば温度を１８０～２５０℃、圧力を４９．０～４９０．３Ｎ／ｃｍ２（５～５０ｋｇｆ／ｃｍ２）、加熱加圧時間を４０～２４０分間にそれぞれ設定することができる。更にこのようにして得られた単層の積層板を内層材として、多層板を作製することができる。この場合、まず積層板にアディティブ法やサブトラクティブ法等にて回路形成を施し、形成された回路表面を酸溶液で処理して黒化処理を施して、内層材を得る。この内層材の、片側又は両側の回路形成面に、樹脂シート、樹脂付き金属箔、又はプリプレグにて絶縁層を形成すると共に、絶縁層の表面に導体層を形成して、多層板を形成するものである。 The composition of the present invention can also be used as a laminated board. When forming a laminated board using a prepreg, one or a plurality of prepregs are laminated, and metal foils are arranged on one side or both sides to form a laminated product, and the laminated material is heated and pressed to integrate the laminated sheets. do. Here, as the metal foil, a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used. As a condition for heating and pressurizing the laminate, it is sufficient to appropriately adjust and heat and pressurize under the condition that the resin composition is cured, but if the pressurizing pressure is too low, air bubbles remain inside the obtained laminate. Since the electrical characteristics may deteriorate, it is preferable to pressurize under conditions that satisfy the moldability. For example, the temperature can be set to 180 to 250 ° C., the pressure can be set to 49.0 to 490.3 N / cm 2 (5 to 50 kgf / cm 2 ), and the heating and pressurizing time can be set to 40 to 240 minutes. Further, a multilayer plate can be produced by using the single-layer laminated plate thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material. An insulating layer is formed from a resin sheet, a metal foil with resin, or a prepreg on the circuit forming surface on one side or both sides of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate. It is a thing.
　また、本発明のビニル硬化性組成物をビルドアップフィルムに使用することもできる。本発明の樹脂組成物からビルドアップフィルムを製造する方法は、例えば、前記樹脂ワニスを、支持フィルム上に塗布、乾燥させてフィルム状の絶縁層を形成する方法が挙げられる。このようにして形成させたフィルム状の絶縁層は、多層プリント配線板用のビルドアップフィルムとして使用できる。 Further, the vinyl curable composition of the present invention can also be used for the build-up film. Examples of the method for producing a build-up film from the resin composition of the present invention include a method in which the resin varnish is applied onto a support film and dried to form a film-shaped insulating layer. The film-shaped insulating layer thus formed can be used as a build-up film for a multilayer printed wiring board.
　本発明の製法によって得られるビニル化合物を配合してなる樹脂組成物の硬化物は、全塩素３０００ｐｐｍ以下、高温でのハロゲンの解離が無く、３．２以下の低誘電率、０．００６以下の低誘電正接を示し、耐熱性にも優れる。特に、フェノール性水酸基を有する化合物としてリン含有フェノール樹脂を使用した場合、難燃性も発現する。 The cured product of the resin composition containing the vinyl compound obtained by the production method of the present invention has a total chlorine of 3000 ppm or less, no halogen dissociation at high temperature, a low dielectric constant of 3.2 or less, and 0.006 or less. It shows low dielectric loss tangent and has excellent heat resistance. In particular, when a phosphorus-containing phenol resin is used as the compound having a phenolic hydroxyl group, flame retardancy is also exhibited.
　次に、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。特に断りがない限り「部」は質量部を表し、「％」は質量％を表す。なお、合成例、実施例中の物性測定は、以下に示す方法により行った。 Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" represents parts by mass and "%" represents% by mass. The physical properties of the synthetic examples and the examples were measured by the methods shown below.
（１）水酸基当量：
　ＪＩＳ　Ｋ　００７０規格に準拠して測定した。具体的には、電位差滴定装置を用い、１、４－ジオキサンを溶剤に用い、１．５ｍｏｌ／Ｌ塩化アセチルでアセチル化を行い、過剰の塩化アセチルを水で分解して０．５ｍｏｌ／Ｌ－水酸化カリウムを使用して滴定した。なお、特に断りがない限り、フェノール樹脂の水酸基当量はフェノール性水酸基当量を意味する。 (1) Hydroxy group equivalent:
Measured according to JIS K 0070 standard. Specifically, using a potentiometric titrator, 1,4-dioxane is used as a solvent, acetylation is performed with 1.5 mol / L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol / L-. Titration was performed using potassium hydroxide. Unless otherwise specified, the hydroxyl group equivalent of the phenol resin means the phenolic hydroxyl group equivalent.
（２）ビニル当量：
　ＪＩＳ　Ｋ　００７０規格に準拠して測定した。具体的には、試料にウィイス液（一塩化ヨウ素溶液）を反応させ、暗所に放置し、その後、過剰の塩化ヨウ素をヨウ素に還元し、ヨウ素分をチオ硫酸ナトリウムで滴定してヨウ素価を算出した。ヨウ素価をビニル当量に換算した。 (2) Vinyl equivalent:
Measured according to JIS K 0070 standard. Specifically, the sample is reacted with a Wies solution (iodine monochloride solution) and left in a dark place, after which the excess iodine chloride is reduced to iodine, and the iodine content is titrated with sodium thiosulfate to determine the iodine value. Calculated. The iodine value was converted to vinyl equivalent.
（３）全塩素：
　試料１．０ｇをブチルカルビトール２５ｍＬに溶解後、１Ｎ－ＫＯＨプロピレングリコール溶液２５ｍＬを加え１０分間加熱還流した後、室温まで冷却し、更に８０％アセトン水１００ｍＬを加え、０．００２Ｎ－ＡｇＮＯ<SUB>３</SUB>水溶液で電位差滴定を行うことにより測定した。
（４）塩素イオン：
  ＪＩＳ　Ｋ　０１２２規格に準拠したイオン電極測定方法によって測定した。具体的には、試料２０ｇに８０％アセトン水１００ｍＬを加え混合した後、酢酸３ｍＬを加え、０．００２Ｎ－ＡｇＮＯ<SUB>３</SUB>水溶液で電位差滴定を行うことにより測定した。 (3) Total chlorine:
After dissolving 1.0 g of the sample in 25 mL of butyl carbitol, add 25 mL of 1N-KOH propylene glycol solution, heat and reflux for 10 minutes, cool to room temperature, add 100 mL of 80% acetone water, and 0.002N-AgNO <SUB. It was measured by performing potentiometric titration with> 3 </ SUB> aqueous solution.
(4) Chloride ion:
The measurement was performed by an ion electrode measuring method conforming to JIS K 0122 standard. Specifically, it was measured by adding 100 mL of 80% acetone water to 20 g of a sample and mixing, adding 3 mL of acetic acid, and performing potentiometric titration with a 0.002N-AgNO <SUB> 3 </ SUB> aqueous solution.
　以下の実施例で使用したビニルアラルキルハライド、フェノール性水酸基を有する化合物は以下の通りである。
・ＣＭＳ：クロロメチルスチレンであり、ｐ－ビニルベンジルクロリドとｍ－ビニルベンジルクロリドの混合物（ＡＧＣセイミケミカル株式会社製、ＣＭＳ－Ｐ）
・ＰＮ：フェノールノボラック樹脂（日鉄ケミカル＆マテリアル株式会社製、ＳＰ－２０６０、水酸基当量１０５ｇ／ｅｑ．、軟化点８５℃）
・ＤＯＰＯ－ＮＱ：１０－（２，７－ジヒドロキシナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド（三光株式会社製、ＨＣＡ―ＮＱ、リン含有率８．３％） The vinyl aralkyl halides and compounds having a phenolic hydroxyl group used in the following examples are as follows.
-CMS: Chloromethylstyrene, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., CMS-P)
PN: Phenolic novolak resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., SP-2060, hydroxyl group equivalent 105 g / eq., Softening point 85 ° C)
DOPO-NQ: 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA-NQ, phosphorus content 8.3%)
実施例１
　撹拌機、パージガス導入口、温度計、冷却管を備えた４口のセパラブルフラスコにＰＮ９７．９部、ジエチレングリコールジメチルエーテル２２９部を仕込み、窒素気流下、撹拌しながら７０℃まで昇温して溶解した。続いてＣＭＳ１４８．１部を仕込み、温度を７０℃から７５℃に保ちながら固形の水酸化カリウム５７．５部を６分割して反応を行った。水酸化カリウムを添加する前にサンプルを取り、水を添加して系内のｐＨをｐＨ試験紙にて確認を行なった。ｐＨが９以上であった場合は反応時間を延長してｐＨが９以下となるまで待ったのち水酸化カリウムを添加した。ガスクロマトグラフィーにて残存ＣＭＳが無いことを確認し反応を終了した。反応時間は６時間であった。温度を維持したまま減圧により溶剤を回収した。得られた樹脂にトルエン５００部を仕込み溶解し、酸により中和した。析出した塩化カリウムを濾過で除去したのち、水洗を行った。３回目の水洗を行った水層の塩素イオンが１０ｐｐｍ以下であったので、水洗を終了し、減圧還流により脱水、脱溶剤を行い、ビニル化合物（Ａ－１）を得た。得られたビニル化合物（Ａ－１）のビニル当量は２３６ｇ／ｅｑ．、全塩素は１２３０ｐｐｍ、収率は９４％であった。 Example 1
97.9 parts of PN and 229 parts of diethylene glycol dimethyl ether were placed in a 4-port separable flask equipped with a stirrer, a purge gas inlet, a thermometer, and a cooling tube, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream to dissolve the flask. .. Subsequently, 148.1 parts of CMS was charged, and 57.5 parts of solid potassium hydroxide was divided into 6 parts to carry out the reaction while keeping the temperature at 70 ° C. to 75 ° C. A sample was taken before adding potassium hydroxide, water was added, and the pH in the system was confirmed with pH test paper. When the pH was 9 or more, the reaction time was extended and the mixture was waited until the pH became 9 or less, and then potassium hydroxide was added. It was confirmed by gas chromatography that there was no residual CMS, and the reaction was terminated. The reaction time was 6 hours. The solvent was recovered by reducing the pressure while maintaining the temperature. 500 parts of toluene was added to the obtained resin, dissolved, and neutralized with an acid. After removing the precipitated potassium chloride by filtration, it was washed with water. Since the chlorine ion of the aqueous layer subjected to the third washing with water was 10 ppm or less, the washing with water was completed, and dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (A-1). The vinyl equivalent of the obtained vinyl compound (A-1) was 236 g / eq. The total chlorine content was 1230 ppm, and the yield was 94%.
実施例２
　実施例１において、空気気流下で反応を行い、固形の水酸化カリウムに代えて５０％水酸化カリウム水溶液を用いた以外は同様な操作を行った。反応時間は１０時間であった。得られたビニル化合物（Ａ－２）のビニル当量は２４１ｇ／ｅｑ、全塩素は１４２０ｐｐｍ、収率は７１％であった。 Example 2
In Example 1, the reaction was carried out under an air flow, and the same operation was performed except that a 50% aqueous potassium hydroxide solution was used instead of the solid potassium hydroxide. The reaction time was 10 hours. The vinyl equivalent of the obtained vinyl compound (A-2) was 241 g / eq, the total chlorine was 1420 ppm, and the yield was 71%.
実施例３
　実施例１と同様な装置にＰＮの代わりにＤＯＰＯ－ＮＱ１２４．１部、ジエチレングリコールジメチルエーテル１２６．７部、ＣＭＳ１２９．６部、固形水酸化カリウム８３．３部、トルエン５２１．３部とした以外は同様な操作を行った。残存ＣＭＳが無いことを確認し反応を終了した。反応は７時間であった。水洗２回目の水層の塩素イオンが５ｐｐｍ以下であったので水洗を終了した。減圧還流により脱水、脱溶剤を行い、ビニル化合物（Ｂ－１）を得た。得られたビニル化合物（Ｂ－１）のビニル当量は２７５ｇ／ｅｑ、全塩素は１３３０ｐｐｍ、収率は８４％であった。 Example 3
The same equipment as in Example 1 except that DOPO-NQ 124.1 parts, diethylene glycol dimethyl ether 126.7 parts, CMS 129.6 parts, solid potassium hydroxide 83.3 parts, and toluene 521.3 parts were used instead of PN. I did a lot of operations. After confirming that there was no residual CMS, the reaction was terminated. The reaction was 7 hours. Since the chlorine ion in the water layer in the second water washing was 5 ppm or less, the water washing was completed. Dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (B-1). The vinyl equivalent of the obtained vinyl compound (B-1) was 275 g / eq, the total chlorine was 1330 ppm, and the yield was 84%.
実施例４
　実施例３において、溶媒としてジエチレングリコールジメチルエーテル単独の代わりにジエチレングリコールジメチルエーテル９１部、トルエン３９部とした以外は同様の操作を行った。残存ＣＭＳが無いことを確認し反応を終了した。反応は９時間であった。水洗２回目の水層の塩素イオンが５ｐｐｍ以下であったので水洗を終了した。減圧還流により脱水、脱溶剤を行い、ビニル化合物（Ｂ－２）を得た。得られたビニル化合物（Ｂ－２）のビニル当量は２７５ｇ／ｅｑ、全塩素は１３５０ｐｐｍ、収率は８２％であった。 Example 4
In Example 3, the same operation was carried out except that 91 parts of diethylene glycol dimethyl ether and 39 parts of toluene were used instead of diethylene glycol dimethyl ether alone as the solvent. After confirming that there was no residual CMS, the reaction was terminated. The reaction was 9 hours. Since the chlorine ion in the water layer in the second water washing was 5 ppm or less, the water washing was completed. Dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (B-2). The vinyl equivalent of the obtained vinyl compound (B-2) was 275 g / eq, the total chlorine was 1350 ppm, and the yield was 82%.
実施例５
　実施例３と同様な操作を行い、析出した塩化カリウムを濾過で除去するところ、水洗により除去を行った。水洗６回目の水層の塩素イオンが５ｐｐｍ以下であったので水洗を終了した。得られたビニル化合物（Ｂ－３）のビニル当量は２７５ｇ／ｅｑ、全塩素は２４５０ｐｐｍ、収率は７４％であった。 Example 5
The same operation as in Example 3 was carried out to remove the precipitated potassium chloride by filtration, which was then removed by washing with water. Since the chlorine ion in the water layer of the 6th water washing was 5 ppm or less, the water washing was completed. The vinyl equivalent of the obtained vinyl compound (B-3) was 275 g / eq, the total chlorine was 2450 ppm, and the yield was 74%.
比較例１
　実施例１と同様な装置にジエチレングリコールジメチルエーテルの代わりにトルエン２２９．０部を仕込んだ以外は同様な操作を行った。固形の水酸化カリウムを添加すると樹脂が析出して撹拌機に付着し撹拌が困難となった。また、実施例１と比較して発熱が激しく長く起きたため冷却を行いながら反応を続けた。析出した樹脂は少しずつ溶解し、反応６時間後の残存ＣＭＳは系内におよそ３％残存していた。更に反応時間を延長し１２時間後でも残存ＣＭＳは変化がなかった。中和を行い、濾過を試みたが粘度が高く減圧吸引濾過できなかった。その為水洗を行った。分液は悪くエマルジョンが発生した。６回目の水洗を行った水層の塩素イオンは１９５ｐｐｍであった。水洗を終了し、減圧還流により脱水、脱溶剤を行い、ビニル化合物（Ａ－Ｈ１）を得た。得られたビニル化合物（Ａ－Ｈ１）のビニル当量は２４４ｇ／ｅｑ、全塩素は４３６０ｐｐｍ、収率は６８％であった。 Comparative Example 1
The same operation was performed except that 229.0 parts of toluene was charged in place of diethylene glycol dimethyl ether in the same apparatus as in Example 1. When solid potassium hydroxide was added, the resin precipitates and adheres to the stirrer, making stirring difficult. In addition, since heat generation was intense and occurred for a long time as compared with Example 1, the reaction was continued while cooling. The precipitated resin was gradually dissolved, and about 3% of the residual CMS remained in the system 6 hours after the reaction. The reaction time was further extended, and the residual CMS did not change even after 12 hours. Neutralization was performed and filtration was attempted, but the viscosity was high and suction filtration under reduced pressure could not be performed. Therefore, it was washed with water. The liquid separation was bad and an emulsion was generated. The chlorine ion in the aqueous layer that was washed with water for the sixth time was 195 ppm. After washing with water, dehydration and solvent removal were carried out by refluxing under reduced pressure to obtain a vinyl compound (AH1). The obtained vinyl compound (A-H1) had a vinyl equivalent of 244 g / eq, total chlorine of 4360 ppm, and a yield of 68%.
比較例２
　比較例１の固形の水酸化カリウムに代えて５０％水酸化カリウム水溶液を用いた以外は同様な操作を行った。比較例１の様な撹拌困難な状態や激しい発熱は見られなかったものの、比較例１と同様に反応６時間後の残存ＣＭＳは系内におよそ３％残存し、反応時間を１２時間に延長しても残存ＣＭＳ量は変化しなかった。得られたビニル化合物（Ａ－Ｈ２）のビニル当量は２３２ｇ／ｅｑ、全塩素は３４６０ｐｐｍ、収率は６５％であった。 Comparative Example 2
The same operation was performed except that a 50% potassium hydroxide aqueous solution was used instead of the solid potassium hydroxide of Comparative Example 1. Although the difficult state of stirring and the intense heat generation as in Comparative Example 1 were not observed, the residual CMS after 6 hours of the reaction remained in the system by about 3% as in Comparative Example 1, and the reaction time was extended to 12 hours. However, the amount of residual CMS did not change. The obtained vinyl compound (A-H2) had a vinyl equivalent of 232 g / eq, total chlorine of 3460 ppm, and a yield of 65%.
比較例３
　実施例２のジエチレングリコールジメチルエーテルの代わりにトルエン８０部、ジエチレングリコールジメチルエーテル５０部とした以外は同様の操作を行った。反応時間は２４時間を要した。水洗では副生物として不溶不融の砂状物が生成した。４回目の水層の塩素イオンが５ｐｐｍ以下であったので水洗を終了した。得られたビニル化合物（Ｂ－Ｈ１）のビニル当量は１９７ｇ／ｅｑ、全塩素は７８３０ｐｐｍ、収率は５２％であった。 Comparative Example 3
The same operation was performed except that 80 parts of toluene and 50 parts of diethylene glycol dimethyl ether were used instead of the diethylene glycol dimethyl ether of Example 2. The reaction time took 24 hours. Washing with water produced insoluble and insoluble sandy substances as by-products. Since the chloride ion of the fourth aqueous layer was 5 ppm or less, the washing with water was completed. The obtained vinyl compound (B-H1) had a vinyl equivalent of 197 g / eq, total chlorine of 7830 ppm, and a yield of 52%.
　実施例１～５、比較例１～３の結果を、まとめて表１に示す。 Table 1 summarizes the results of Examples 1 to 5 and Comparative Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
　本発明の製造方法によって高収率で得られるビニル基含有芳香族エーテル化合物は、電子・電気材料分野、特にスマートフォンに代表される電子機器において低誘電性が要求される回路基板材料などのラジカル重合性樹脂成分として好適に利用できる。
  The vinyl group-containing aromatic ether compound obtained in high yield by the production method of the present invention is radically polymerized in the field of electronic and electrical materials, especially circuit substrate materials that require low dielectric constant in electronic devices such as smartphones. It can be suitably used as a sex resin component.

Claims (12)

  1. 　フェノール性水酸基を有する化合物と下記一般式（１）で表されるビニルアラルキルハライドとを塩基性を示すアルカリ（土類）金属化合物の存在下、反応溶媒中で反応させてビニル基を有するエーテル化合物を製造するにあたり、ジエチレングリコールジメチルエーテルを５０質量％以上含む反応溶媒を使用して反応を行うことを特徴とするビニル基含有芳香族エーテル化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000001
      
    ここで、Ａｒ１は芳香族環基であり、Ｘはハロゲン原子である。     An ether compound having a vinyl group by reacting a compound having a phenolic hydroxyl group with a vinyl aralkyl halide represented by the following general formula (1) in a reaction solvent in the presence of an alkaline (earth) metal compound showing basicity. A method for producing a vinyl group-containing aromatic ether compound, which comprises using a reaction solvent containing 50% by mass or more of diethylene glycol dimethyl ether to carry out the reaction.
    Figure JPOXMLDOC01-appb-C000001
    Here, Ar 1 is an aromatic ring group and X is a halogen atom.
  2. 　アルカリ（土類）金属化合物が固形のアルカリ（土類）金属水酸化物又はアルカリ（土類）金属炭酸塩であり、非水系で反応を行う請求項１に記載の製造方法。 The production method according to claim 1, wherein the alkaline (earth) metal compound is a solid alkali (earth) metal hydroxide or an alkali (earth) metal carbonate, and the reaction is carried out in a non-aqueous system.
  3. 　固形アルカリ（土類）金属化合物を分割添加する請求項２に記載の製造方法。 The production method according to claim 2, wherein the solid alkali (earth) metal compound is added in portions.
  4. 　不活性ガス雰囲気下で反応を行う請求項１に記載の製造方法。 The production method according to claim 1, wherein the reaction is carried out in an atmosphere of an inert gas.
  5. 　反応により生成したハロゲン化アルカリ（土類）金属を、ろ過により除去したのち水洗を行う請求項１に記載の製造方法。 The production method according to claim 1, wherein the alkali halide (earth) metal generated by the reaction is removed by filtration and then washed with water.
  6. 　フェノール性水酸基を有する化合物が下記一般式（２）で表されるリン含有フェノール化合物である請求項１に記載の製造方法。
    Figure JPOXMLDOC01-appb-C000002
      ここで、Ｒ１及びＲ２はそれぞれ独立に炭素数１～１５の酸素原子を有してもよい炭化水素基であり、Ｒ１とＲ２で環状構造を形成していてもよい。Ａ２は芳香族環基である。     The production method according to claim 1, wherein the compound having a phenolic hydroxyl group is a phosphorus-containing phenol compound represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000002
     Here, R 1 and R 2 are hydrocarbon groups that may independently have oxygen atoms having 1 to 15 carbon atoms, and R 1 and R 2 may form a cyclic structure. A 2 is an aromatic ring group.
  7. 　フェノール性水酸基を有する化合物が、フェノール性水酸基を２以上有するフェノール化合物である請求項１に記載の製造方法。 The production method according to claim 1, wherein the compound having a phenolic hydroxyl group is a phenol compound having two or more phenolic hydroxyl groups.
  8. 　請求項１に記載の製造方法によりビニル基含有芳香族エーテル化合物を得ること、このビニル基含有芳香族エーテル化合物にラジカル開始剤を必須成分として配合することを特徴とする樹脂組成物の製造方法。 A method for producing a resin composition, which comprises obtaining a vinyl group-containing aromatic ether compound by the production method according to claim 1, and blending the vinyl group-containing aromatic ether compound with a radical initiator as an essential component.
  9. 　請求項１に記載の製造方法によりビニル基含有芳香族エーテル化合物を得ること、このビニル基含有芳香族エーテル化合物にラジカル開始剤を必須成分として配合して樹脂組成物とすること、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物をラジカル重合させることを特徴とする芳香族エーテル系樹脂の製造方法。 To obtain a vinyl group-containing aromatic ether compound by the production method according to claim 1, to prepare a resin composition by blending the vinyl group-containing aromatic ether compound with a radical initiator as an essential component, the vinyl group-containing. A method for producing an aromatic ether-based resin, which comprises radically polymerizing an aromatic ether compound or a resin composition.
  10. 　請求項１に記載の製造方法によりビニル基含有芳香族エーテル化合物を得ること、このビニル基含有芳香族エーテル化合物にラジカル開始剤を必須成分として配合して樹脂組成物とすること、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物に繊維質基材を配合して半硬化させることを特徴とするプリプレグの製造方法。 Obtaining a vinyl group-containing aromatic ether compound by the production method according to claim 1, blending the vinyl group-containing aromatic ether compound with a radical initiator as an essential component to obtain a resin composition, and containing the vinyl group. A method for producing a prepreg, which comprises blending a fibrous base material with an aromatic ether compound or a resin composition and semi-curing it.
  11. 　請求項１に記載の製造方法によりビニル基含有芳香族エーテル化合物を得ること、このビニル基含有芳香族エーテル化合物にラジカル開始剤を必須成分として配合して樹脂組成物とすること、前記ビニル基含有芳香族エーテル化合物又は樹脂組成物を樹脂フィルムに塗布し、半硬化させることを特徴とする樹脂シートの製造方法。 To obtain a vinyl group-containing aromatic ether compound by the production method according to claim 1, to prepare a resin composition by blending the vinyl group-containing aromatic ether compound with a radical initiator as an essential component, the vinyl group-containing. A method for producing a resin sheet, which comprises applying an aromatic ether compound or a resin composition to a resin film and semi-curing it.
  12. 　請求項１０に記載のプリプレグの製造方法又は請求項１１に記載の樹脂シートの製造方法によりプリプレグ又は樹脂シートを得ること、次いでこのプリプレグ又は樹脂シートを積層し、成形することを特徴とする積層板の製造方法。
     
          A laminated plate characterized by obtaining a prepreg or a resin sheet by the method for producing a prepreg according to claim 10 or the method for producing a resin sheet according to claim 11, and then laminating and molding the prepreg or the resin sheet. Manufacturing method.
PCT/JP2021/031623 2020-09-10 2021-08-27 Method for producing aromatic ether compound having vinyl group WO2022054614A1 (en)

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