Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

• the present invention is used as an insulating material for electrical and electronic parts such as highly reliable semiconductor encapsulation, various composite materials such as laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastics), molding raw materials, and the like. It relates to a useful poly (vinylbenzyl) ether compound, a method for producing the same, a composition containing the poly (vinylbenzyl) ether compound, and a cured product thereof.
• curable resins are widely used for adhesion, casting, coating, impregnation, lamination, molding compounds, and the like.
• its applications have been diversified in recent years, and depending on the usage environment and usage conditions, conventionally known curable resins may not be sufficient.
• laminated boards used in various electric devices are required to have high performance such as high heat resistance with the progress of electronic devices in recent years.
• a curable resin having excellent electrical characteristics such as a low dielectric constant and a low dielectric loss tangent, in order to increase the calculation speed and propagation speed of a computer and to increase the frequency of mobile communication equipment and the like.
• Patent Documents 1 to 3 examples of the matrix resin of the laminated board that are mainly put into practical use include phenol resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, and polyimide resin, and these resins have high heat resistance and the like.
• Patent Documents 1 to 3 the requirements were satisfied (Patent Documents 1 to 3), the low dielectric constant and the low dielectric addict were not sufficiently satisfied.
• Vinyl benzyl ether compounds are described in Patent Documents 4 to 6 as a solution to such a problem, and the dielectric properties of the cured product described in these patent documents sufficiently satisfy the performance currently required. It has not been achieved.
• Patent Document 7 describes a resin structure that further improves the dielectric properties, but the thermal conductivity of the described cured product does not sufficiently achieve the performance currently required.
• the present invention provides a cured product that exhibits heat resistance, low dielectric constant, low dielectric adduct, and high thermal conductivity, and is an insulating material for electrical and electronic parts such as semiconductor encapsulation, which requires high reliability, and laminated plates.
• the present invention is a poly (vinylbenzyl) ether compound represented by the following formula (1), wherein 90% or more of the substitution positions of the vinyl group at the vinylbenzyl moiety is in the para position.
• Vinylbenzyl) Ether compound represented by the following formula (1), wherein 90% or more of the substitution positions of the vinyl group at the vinylbenzyl moiety is in the para position.
• R 1 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group, and the proportion of the alkyl group in all R1 is 0.1 to 40 mol%, and the vinylbenzyl group. The ratio of is 60 to 99.9 mol%.
• R 2 independently represents an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms
• R 3 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• Ar 1 and Ar 2 represent an aromatic ring group having 6 to 50 carbon atoms.
• n is an average value in the range of 1 to 20.
• m is an integer of 0 to 6
• r is an integer of 1 to 3
• m + r does not exceed 8.
• k is 0 or 1.
• the present invention is a curable resin composition
• a curable resin composition comprising the above poly (vinylbenzyl) ether compound and a radical polymerization initiator.
• the present invention is a cured product obtained by curing the above curable resin composition.
• the present invention is a curable composite material composed of the curable resin composition and a base material.
• the present invention is a cured composite material obtained by curing the above-mentioned curable composite material.
• the present invention is a laminate characterized by having a layer of the cured composite material and a metal foil layer.
• the present invention is a metal leaf with a resin, characterized in that a film formed from the curable resin composition is provided on one side of the metal leaf.
• the present invention is a method for producing the above-mentioned poly (vinyl benzyl) ether compound, which is obtained by reacting a phenol resin represented by the following formula (2) with a vinyl aromatic halomethyl compound.
• (Vinylbenzyl) A method for producing an ether compound.
• R 4 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the hydrogen atom in all R 4 is 60 to 99.9 mol%.
• R 2 , R 3 , Ar 1 , Ar 2 , n, m, r, and k are synonymous with those in the equation (1).
• the poly (vinylbenzyl) ether compound of the present invention provides a cured product having excellent heat resistance, low dielectric constant, low dielectric loss tangent, and high thermal conductivity as compared with the conventional vinylbenzyl ether compound. Therefore, the poly (vinylbenzyl) ether compound of the present invention is extremely useful for applications such as electric / electronic materials, laminated materials, molding materials, and casting materials.
• the poly (vinylbenzyl) ether compound of the present invention is represented by the above formula (1).
• R 1 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group.
• the proportion (mol%) of the vinylbenzyl group in the total R1 is 60 to 99.9 mol%.
• the proportion of the vinylbenzyl group (mol%) is preferably 70 to 99 mol%, more preferably 75 to 95 mol%, and particularly preferably 75 to 92 mol%.
• the proportion (mol%) of the alkyl group in the total R1 is 0.1 to 40 mol%.
• the proportion of the alkyl group is preferably 1 to 30 mol%, more preferably 2 to 30 mol%, still more preferably 3 to 30 mol%, and particularly preferably 5 to 25 mol%. Further, although hydrogen atoms may be present, the ratio of the hydroxyl group ratio is preferably 10 mol% or less, more preferably 5 mol% or less. If there are many hydrogen atoms, the dielectric properties may deteriorate.
• the alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic.
• branched-chain or cyclic alkyl groups tend to give higher heat resistance than linear ones.
• the number of carbon atoms is preferably 1 to 4 in the case of a chain-like alkyl group, and preferably 6 in the case of a cyclic alkyl group.
• a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a t-butyl group and a cyclohexyl group are preferable, and a methyl group, an ethyl group, an n-propyl group and a t-butyl group are more preferable.
• Ar 3 is a phenylene group or a substituted phenylene group.
• substituent in the case of the substituted phenylene group include an alkyl group, an alkoxy group and a phenyl group. Preferred are alkyl groups having 1 to 6 carbon atoms.
• Ar 3 is more preferably an unsubstituted, alkyl group-substituted, alkoxy group-substituted, or phenyl group-substituted phenylene group.
• r represents an integer of 1 to 3, but is preferably 1 or 2 from the viewpoint of solubility and toughness.
• the substituent R 2 of Ar 1 independently represents an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms.
• the aryl group may further have a substituent such as an alkyl group having 1 to 6 carbon atoms.
• a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms (more preferably 6 carbon atoms) is preferable. It is a group, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• m is the number of the substituent R 2 of Ar 1 and represents an integer of 0 to 6.
• m is preferably 1 or 2 from the viewpoint of the balance between solubility and flame retardancy.
• m + r is 8 or less, but preferably 1 to 4.
• the alkyl group having 1 to 6 carbon atoms represents a linear, branched or cyclic alkyl group.
• a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group and the like can be mentioned.
• branched-chain or cyclic alkyl groups tend to give higher heat resistance than linear ones.
• the number of carbon atoms is preferably 1 to 4 in the case of a chain-like alkyl group, and preferably 6 in the case of a cyclic alkyl group.
• an isopropyl group, an isobutyl group, a t-butyl group and a cyclohexyl group are preferable, and a t-butyl group and a cyclohexyl group are more preferable. Further, a methyl group is also preferable because the flame retardancy tends to be improved.
• R 3 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• alkyl group having 1 to 6 carbon atoms are the same as those of R2 above, and the preferred group is also the same.
• Ar 1 represents an aromatic ring group having 6 to 50 carbon atoms.
• it is an aromatic ring group selected from a benzene ring, a naphthalene ring, a biphenyl ring, or a bisphenyl structure, and has a structure in which two hydroxyl groups are removed from an aromatic diol compound.
• Ar 1 is preferably a naphthalene ring or a biphenyl ring, and more preferably a naphthalene ring.
• aromatic diol compound examples include dihydroxybenzenes such as hydroquinone, resorcin, and catechol, dihydroxynaphthalene, biphenol, bisphenol A, bisphenol acetophenone, bisphenol AF, bisphenol AD, bisphenol B, bisphenol BP, and bisphenol C.
• aromatic diol compound examples include bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol trimethylcyclohexane, bisphenol cyclohexane, bisphenol cyclododecane, bisphenol fluorene, oxybisphenol, thiobisphenol and the like.
• Ar 2 represents an aromatic ring group having 6 to 50 carbon atoms.
• aromatic rings (Ph, Np, and Flu) Selected from the group consisting of -Ph-, -Ph-Flu-Ph-, -Np-, -Np-Np-, -Np- CH2 -Np-, and -Np-Flu-Np-
• aromatic rings (Ph, Np, and Flu) further have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of carbon atoms as substituents.
• Ph represents a phenylene group (-C 6 H 4- )
• Np represents a naphthylene group (-C 10 H 6- )
• Flu represents a fluorenyl group (-C 13 H 8- ).
• Ar 2 is more preferably unsubstituted, alkyl group substituted, alkoxy group substituted, or phenyl group substituted -Ph-, -Ph-Ph- (biphenylene group), or -Np-, and even more preferably none. Substitution, alkyl group substitution, alkoxy group substitution, or phenyl group substitution -Ph- or -Ph-Ph-.
• the alkyl group or alkoxy group having 1 to 6 carbon atoms of the Ar 2 substituent may be linear, branched or cyclic.
• Examples of the aryl group or aryloxy group having 6 to 12 carbon atoms of the Ar 2 substituent include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a propylphenyl group, a trimethylphenyl group, a naphthyl group, an indanyl group and a phenoxy group.
• Examples thereof include a trilloxy group, an ethylphenoxy group, a xsilyloxy group, a propylphenoxy group, a trimethylphenoxy group, a naphthyloxy group and the like.
• Examples of the aralkyl group or aralkyloxy group having 7 to 12 carbon atoms of the Ar 2 substituent include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a phenethyl group, a 1-phenylethyl group and a 2-phenylisopropyl group.
• Examples thereof include a naphthylmethyl group, a benzyloxy 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.
• n represents a number of 1 to 20 on average, preferably 1 to 10. If n exceeds 20, the viscosity may increase and the filling property into the fine pattern may decrease. When it has a molecular weight distribution, it is a number average value.
• the poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention has a peak area derived from the vinyl aromatic halomethyl compound as a raw material for production in gel permeation chromatography (GPC) measurement.
• the total peak area including the peak area of the benzyl) ether compound is preferably 1.0% or less, more preferably 0.5% or less, still more preferably 0.2% or less. If the residual amount of the vinyl aromatic halomethyl compound is large, the deterioration of the dielectric property after being subjected to a heat history of 250 ° C. or higher for a long time may be large.
• the peak area of the poly (vinylbenzyl) ether compound means the peak area based on the pure poly (vinylbenzyl) ether compound.
• the poly (vinylbenzyl) ether compound of the present invention is a reaction product or a purified product thereof, and contains a small amount of other components in addition to the pure poly (vinylbenzyl) ether compound.
• the poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention is obtained by reacting the phenol resin represented by the above formula (2) with a vinyl aromatic halomethyl compound.
• R 2 , R 3 , Ar 1 , Ar 2 , n, m, r, and k are R 2 , R 3 , Ar 1 , Ar 2 , n, m in the above formula (1). It is synonymous with r and k.
• the above R 4 independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the proportion (mol%) of the alkyl group in all R 4 is 0.1 to 40 mol%, preferably 1 to 30 mol. %, More preferably 3 to 25 mol%.
• the method for producing the phenolic resin represented by the formula (2) is not particularly limited, and for example, Patent Documents 1 to 3, JP-A-2001-213946, JP-A-11-255868, and JP-A-11.
• Patent Documents 1 to 3 JP-A-2001-213946, JP-A-11-255868, and JP-A-11.
• Japanese Patent Laid-Open No. 228673 Japanese Patent Application Laid-Open No. 08-073570, Japanese Patent Application Laid-Open No. 08-048755, Japanese Patent Application Laid-Open No. 10-310634, JP-A-11-116647, etc.
• phenols and condensing agents are used. It can be obtained by removing unreacted phenols and impurities after the condensation reaction.
• the raw material phenols are compounds having at least one phenolic hydroxyl group on the benzene ring, and have an alkyl group having 1 to 6 carbon atoms, an allyl group, or 1 to 4 substituents which are aryl groups. You may.
• Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group, and an isopropyl group.
• Branched alkyl groups such as sec-butyl group, t-butyl group, isobutyl group, isopentyl group, neopentyl group, t-pentyl group and isohexyl group, and cyclic alkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
• the group etc. can be mentioned.
• Examples of the aryl group include a phenyl group and a naphthyl group.
• phenols include phenol, cresol, pentylphenol, phenylphenol, resorcinol, ⁇ -naphthol, ⁇ -naphthol, naphthalenediol, 2-methyl-1-naphthol, 3-methyl-2-naphthol, and tri.
• examples thereof include hydroxynaphthalene and biphenol. These may be used alone or may use two or more kinds. From the viewpoint of solubility, flame retardancy and availability of raw materials, ⁇ -naphthol, ⁇ -naphthol, or naphthalenediol is preferable.
• the compound represented by the above formula (2) becomes a naphthol resin, but in the present specification, these resins are also referred to as a phenol resin.
• the raw material condensing agent is an aldehyde, a ketone, or an aromatic compound represented by the following formula (3) or formula (4).
• k is 0 in the formulas (1) and (2), and when an aromatic compound represented by the formula (3) or the formula (4) is used, k is 1. be.
• R 3 and Ar 2 are synonymous with R 3 and Ar 2 in the above formula (1)
• Y is a condensation active group, and a fluorine atom, a chlorine atom, a bromine atom, It represents a methoxy group, an ethoxy group, or a hydroxyl group, and is preferably a methoxy group, a chlorine atom, or a hydroxyl group from the viewpoint of ease of condensation and availability of a raw material.
• aldehydes and ketones examples include formaldehyde, acetaldehyde, benzaldehyde, and acetone.
• aldehydes and ketones examples include formaldehyde, acetaldehyde, benzaldehyde, and acetone.
• aromatic compound represented by the formula (3) examples include 4,4'-bis (fluoromethyl) -1,1'-biphenyl and 4,4'-bis (chloromethyl) -1,1'-.
• Biphenyl 4,4'-bis (bromomethyl) -1,1'-biphenyl, 4,4'-bis (hydroxymethyl) -1,1'-biphenyl, 4,4'-bis (hydroxyethyl) -1, 1'-biphenyl, di (chloromethyl) benzene, di (bromomethyl) benzene, di (chloromethyl) naphthalin, di (chloromethyl) biphenyl ether, xylylene glycol, xylylene glycol dimethyl ether, xylylene glycol diethyl ether, xylylene Examples thereof include xylylene glycol mono such as glycol dipropyl ether, xylylene glycol dibutyl ether, xylylene glycol monomethyl ether and xylylene glycol monoethyl ether, dilower alcohol ether and the like, dichloromethylnaphthalene and dimethoxynaphthalene
• xylylene glycol preferably xylylene glycol, xylylene glycol dimethyl ether, dichloromethylbenzene, or 4,4'-bis (chloromethyl) -1,1'-biphenyl, and more preferably xylylene glycol dimethyl ether.
• aromatic compound represented by the formula (4) include divinylbenzene, divinylnaphthalene, 4,4'-divinyl-1,1'-biphenyl and the like. Preferred is divinylbenzene.
• the amount of the condensing agent used is usually 0.1 to 0.9 mol, preferably 0.15 to 0.7 mol, based on 1 mol of the phenols.
• an acid catalyst can be used in the reaction between the phenols and the condensing agent.
• the acid catalyst include organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid and oxalic acid; and Friedelcraft catalysts such as ferrous chloride, zinc chloride and ferric chloride. Not limited to. Of these, sulfuric acid, p-toluenesulfonic acid and stannous chloride are preferable, but p-toluenesulfonic acid is particularly preferable in the production method of the present invention.
• the amount of these acid catalysts used varies depending on the type of catalyst, but it is preferably used in the range of 0.0005 to 10% by mass with respect to the condensing agent.
• the reaction temperature in the reaction between the phenols and the condensing agent is usually 40 to 200 ° C, preferably 50 to 150 ° C.
• the reaction time is 0.5 to 20 hours, preferably 1 to 15 hours.
• the reaction may be carried out by charging all the raw materials at once and raising the temperature, or by sequentially adding a condensing agent while keeping the phenols at a constant temperature in advance.
• an organic compound such as toluene, monochlorobenzene, dichlorobenzene, or a lower alcohol such as methanol, ethanol, propanol and butanol, which is not directly involved in the reaction, can also be used as a solvent.
• Hydrochloric acid gas generated during the reaction depending on the type of condensing agent used may be removed from the system by flowing an inert gas such as nitrogen gas, or may be removed under reduced pressure.
• the phenol resin represented by the formula (2) can be obtained. Recovery of unreacted phenols and solvents is preferably carried out under normal pressure or reduced pressure. It is also possible to blow steam and distill off by steam distillation.
• the temperature for distillation recovery of phenols is 100 to 180 ° C., and the degree of decompression is preferably about 0.1 to 25 kPa.
• the obtained phenol resin represented by the formula (2) is reacted with a vinyl aromatic halomethyl compound to synthesize a poly (vinylbenzyl) ether compound.
• the reaction between the phenol resin represented by the formula (2) and the vinyl aromatic halomethyl compound is not particularly limited.
• a method of reacting a phenol resin and a vinyl aromatic halomethyl compound in a polar solvent using an alkali metal hydroxide as a dehydrohalogenating agent can be mentioned.
• a reaction product containing a poly (vinylbenzyl) ether compound is obtained, and this is purified by washing with water.
• it may be purified with a mixed solvent consisting of water and alcohols.
• the reaction between the phenol resin and the vinyl aromatic halomethyl compound is carried out, for example, by reacting in the liquid phase in the presence of an alkali metal hydroxide.
• the hydroxyl group of the phenol resin and the -CH 2 X group (X is a halogen atom) of the vinyl aromatic halomethyl compound undergo a condensation reaction to cause de-HX and formation of an -O-CH 2- bond, resulting in poly (vinyl).
• a benzyl) ether compound is produced.
• some of the phenolic hydroxyl groups of the phenolic resin represented by the formula (2) are, for example, alcohols having 1 to 12 carbon atoms in the presence of an acidic catalyst. By reacting, an alkyl group having 1 to 12 carbon atoms can be introduced in R4 of the formula (2) to make it alkoxylated.
• the reaction of introducing an alkyl group and alkoxylating may be before or after the reaction with the vinyl aromatic halomethyl compound, but it is preferable before the reaction in order to avoid the polymerization of the vinyl group. ..
• a partially alkoxylated phenolic resin (partially modified phenolic resin) in which a part of the hydrogen atom of the hydroxyl group is substituted with an alkyl group is first synthesized, and then reacted with a vinyl aromatic halomethyl compound to partially prepare it. This is a method for obtaining an alkoxylated poly (vinylbenzyl) ether compound.
• the phenols For a part or all of the raw material of the phenol resin, as the phenols, those having a part or all of the hydroxyl group as an alkoxy group can be used, and these can be used in combination with the phenols in which the hydroxyl group is not modified. ..
• a hydroxyl group having a part of the hydroxyl group as an alkoxy group is used, it is not necessary to use phenols in which the hydroxyl group is not denatured.
• the phenol resin may be a mixture of one in which all of the hydroxyl groups are alkoxylated and one in which all of the hydroxyl groups remain.
• the hydroxyl group equivalent (g / eq.) Of the phenol resin is preferably 200 to 400, more preferably 220 to 350.
• Ar 3 is a phenylene group or a substituted phenylene group.
• substituent in the case of the substituted phenylene group include an alkyl group, an alkoxy group and a phenyl group. Preferred are alkyl groups having 1 to 6 carbon atoms.
• Ar 3 is more preferably an unsubstituted, alkyl group-substituted, alkoxy group-substituted, or phenyl group-substituted phenylene group.
• X is a halogen atom, and a chlorine atom or a bromine atom is preferable.
• Preferred vinyl aromatic halomethyl compounds include, for example, p-vinylbenzyl chloride, m-vinylbenzyl chloride, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide. , A mixture of p-vinylbenzyl bromide and m-vinylbenzyl bromide, and the like. Of these, at least one selected from the group consisting of p-vinylbenzyl chloride and m-vinylbenzyl chloride is preferable.
• the composition ratio of the p-vinyl aromatic halomethyl compound (p-form) is preferably 90 to 100 mol%, more preferably 91 to 99 mol%, still more preferably 92 to 98 mol%.
• the amount of the vinyl aromatic halomethyl compound used can be appropriately adjusted, but the vinyl aromatic halomethyl compound is 0.4 to 1.20 with respect to 1 mol of the phenolic hydroxyl group of the phenol resin.
• the moles are preferable, and 0.95 to 1.10 moles are more preferable.
• an amount close to the total amount of the charged phenol resin reacts with the vinyl aromatic halomethyl compound, and the phenolic hydroxyl group in the phenol resin is converted to vinylbenzyl ether and almost remains in the reaction product. It is preferable because it disappears, the curing reaction to be performed later proceeds sufficiently, and good dielectric properties are exhibited.
• the charged molar ratio may be adjusted as appropriate to leave phenolic hydroxyl groups.
• a polar solvent in order to improve the solubility.
• the polar solvent include alcohols such as methanol, ethanol, propanol and butanol, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dioxane, tetrahydrofuran, ethyleneglycoldimethylether and diethyleneglycoldimethylether, 1, Ethereal solvents such as 3-dimethoxypropane and 1,2-dimethoxyethane, ketone solvents such as acetone, methylethylketone, methylisobutylketone and cyclohexanone, dimethylsulfoxide, acetonitrile, tetramethylenesulfone, hexamethylphosphoamide and the like are used. The examples are not limited to these. These may be used alone or may use two or more kinds. The amount of
• alkali metal hydroxide When carrying out this reaction, an alkali metal hydroxide is often used to promote the reaction, and preferred alkali metal hydroxides include sodium hydroxide, potassium hydroxide, or a mixture thereof.
• the alkali metal hydroxide may be used as an aqueous solution, in which case the alkali metal hydroxide can be continuously added.
• the amount of the alkali metal hydroxide used is preferably 0.6 to 2.0 mol, more preferably 0.9 to 1.8 mol, and 1.0 to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound. ⁇ 1.7 is more preferable.
• reaction temperature and reaction time of this reaction may be appropriately selected according to the reaction, but the reaction proceeds sufficiently if they are in the range of 30 to 100 ° C. and 0.5 to 20 hours, respectively. Further, the reaction end point can be confirmed by measuring the remaining vinyl aromatic halomethyl compound by gas chromatography.
• phase transfer catalyst As another reaction method, in the presence of an interphase transfer catalyst, a phenol resin and a vinyl aromatic halomethyl compound are reacted in a mixed solution of water and an organic solvent using an alkali metal hydroxide as a dehydrogenated halide agent. This produces a poly (vinylbenzyl) ether compound.
• the phase transfer catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, and tetran-butylammonium bromide.
• the amount of the quaternary ammonium salt used is usually 0.001 to 0.2 mol, preferably 0.002 to 0.15 mol, and more preferably 0.01 to 0.12 mol with respect to 1 mol of the hydroxyl group of the phenol resin. It is mol, more preferably 0.05 to 0.1 mol.
• the obtained reaction product is a crude poly (vinylbenzyl) ether compound containing the poly (vinylbenzyl) ether compound of the formula (1).
• reprecipitation purification is performed by adjusting the amount of the vinyl aromatic halomethyl compound used or by using other means, for example, a poor solvent.
• unreacted raw materials and the like may be removed by purification by recrystallization.
• the poor solvent those having low solubility of poly (vinylbenzyl) ether compounds and high solubility of halogen compounds are suitable.
• a poor solvent include methanol, ethanol, isopropanol, ethylene glycol, water, or a mixed solvent thereof, and a mixed solvent of water and alcohols is preferable.
• Suitable as such a poor solvent is a polar solvent having a solubility parameter of 10 or more, and more preferably a polar solvent having a solubility parameter of 11 or more.
• the solubility parameter value in the range of 15 to 20 is most preferable from the viewpoint of the recovery yield of the poly (vinylbenzyl) ether compound and the purification efficiency of reducing the remaining vinyl aromatic halomethyl compound.
• the curable resin composition of the present invention contains the poly (vinylbenzyl) ether compound of the present invention and a radical polymerization initiator (also referred to as a radical polymerization catalyst).
• a radical polymerization initiator also referred to as a radical polymerization catalyst.
• the resin composition of the present invention undergoes a cross-linking reaction by means such as heating to be cured as described later, but the reaction temperature at that time is lowered or the cross-linking reaction of unsaturated groups is carried out. May be used by containing a radical polymerization initiator for the purpose of accelerating.
• radical polymerization initiators are benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (). t-butylperoxy) hexane-3, di-t-butyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl- 2,5-Di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, Peroxides such as 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy)
• 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst).
• the catalyst and radical polymerization initiator used for curing the present resin composition are not limited to these examples.
• the amount of the radical polymerization initiator to be blended is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the poly (vinylbenzyl) ether compound of the present invention and the poly (vinylbenzyl) ether compound that can be used in combination and the copolymerizable compound. Within the range of the part, the reaction proceeds satisfactorily without inhibiting the curing reaction. It is preferably 0.05 to 9 parts by mass, and more preferably 0.1 to 8 parts by mass.
• the curable resin composition of the present invention may be used in combination with the poly (vinylbenzyl) ether compound of the present invention and a copolymerizable compound.
• Examples of the compound that can be used in combination with the poly (vinylbenzyl) ether compound of the present invention and can be copolymerized with the poly (vinylbenzyl) ether compound include styrene, styrene dimer, alphamethylstyrene, alphamethylstyrene dimer, divinylbenzene, and vinyl.
• Toluene, t-butylstyrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, acenaphtylene, divinylbenzyl ether, allylphenol, allylphenyl ether, diallylphthalate, acrylic acid ester, methacrylic acid ester, vinylpyrrolidone and the like can be mentioned. Yes, but not limited to these. These may be used alone or may use two or more kinds. The blending ratio of these compounds is about 2 to 50 parts by mass with respect to 100 parts by mass of the poly (vinylbenzyl) ether compound.
• Hydroquinone, benzoquinone, copper salt, etc. can be blended as a stabilizer for adjusting the degree of curing.
• a curing accelerator When using a radical polymerization initiator, a curing accelerator may be used in combination.
• the curing accelerator that can be used in combination include imidazoles such as 2-methylimidazole, 2-ethyl imidazole, 2-phenyl imidazole, and 2-ethyl-4-methyl imidazole; 2- (dimethylaminomethyl) phenol, triethylenediamine, and the like.
• Tertiary amines such as triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; organic phosphines such as triphenylphosphine, diphenylphosphine, tributylphosphine, and metal compounds such as tin octylate.
• Tetra-substituted phosphonium-tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholin / tetraphenylborate.
• Etc., tetraphenylboron salts and the like can be mentioned.
• the amount used is 0.01 to 15 with respect to a total of 100 parts by mass of the compound that can be copolymerized with the poly (vinylbenzyl) ether compound that can be used in combination with the poly (vinylbenzyl) ether compound. Mass parts are used as needed.
• the curable resin composition of the present invention may contain various compounding agents such as inorganic fillers, silane coupling agents, stabilizers, mold release agents, pigments, various thermosetting resins / thermoplastic resins, if necessary. Reinforcing fibers can be added.
• examples of the inorganic filler include silica, alumina, zirconia, titanium dioxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, silicon nitride, aluminum nitride, silica soil, mica, potassium titanate whiskers, and bathium titanate whiskers.
• examples include, but are not limited to, zinc oxide whisker. These may be used alone or may use two or more kinds.
• thermosetting resin examples include vinyl ester resin, polyvinyl benzyl resin, unsaturated polyester resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin and the like.
• thermoplastic resin examples include polystyrene, polyphenylene ether, polyetherimide, polyethersulfone, PPS resin, polycyclopentadiene resin, polycycloolefin resin and the like.
• thermoplastic elastomer examples include styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, and water.
• examples thereof include a styrene-isoprene copolymer.
• it can also be blended with rubbers such as polybutagen and polyisoprene. These may be used alone or may use two or more kinds.
• the amount to be used is about 0.01 to 90 parts by mass with respect to a total of 100 parts by mass of the compound that can be copolymerized with the poly (vinylbenzyl) ether compound that can be used in combination with the poly (vinylbenzyl) ether compound. Is used.
• reinforcing fiber examples include, but are not limited to, glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber and the like. These may be used alone or may use two or more kinds.
• the curable resin composition of the present invention can be obtained by uniformly mixing each of the above components.
• the polymerization and curing of the curable resin composition of the present invention can be carried out by a known method. Curing can be performed in the presence or absence of a curing agent, and if necessary, for example, a curing accelerator and an inorganic filler, a compounding agent, various thermosetting resins / thermoplastic resins, reinforcing fibers, and the like can be used. If necessary, use an extruder, kneader, blender, roll, or the like to sufficiently mix until uniform to obtain the curable resin composition of the present invention.
• the curable resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like.
• the curing temperature cannot be unconditionally specified because it varies depending on the presence or absence of the curing agent and the type of the curing agent, but it is 20 to 250 ° C., preferably 50 to 230 ° C., 0.5 to 10 hours, preferably 1 to 8 ° C.
• the cured product of the present invention can be obtained by heating for an hour. If the temperature is less than 20 ° C., sufficient curing cannot be obtained.
• the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. and is a reinforcing fiber such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber. It is also possible to obtain the cured product of the present invention by hot press molding the prepreg obtained by impregnating the base material such as the above and heating and drying.
• a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
• a reinforcing fiber such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber.
• the cured product of the present invention can also be obtained.
• the curable resin composition of the present invention dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone can also be used as a varnish, a paint, and an adhesive.
• the amount of the solvent used at this time is usually 5 to 90% by mass, preferably 10 to 80% by mass, based on the total amount of the curable resin composition and the solvent of the present invention.
• a flame retardant-imparting agent in combination with the curable resin composition of the present invention, electrical or electronic component materials that are required to have dielectric properties, flame retardancy, or heat resistance, particularly semiconductor encapsulation materials and circuit boards. It can be used especially useful as a varnish.
• the varnish for circuit board material can be produced by dissolving the curable resin composition of the present invention in a solvent such as toluene, xylene, tetrahydrofuran and dioxolane.
• a solvent such as toluene, xylene, tetrahydrofuran and dioxolane.
• Specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.
• the cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film.
• the cured product of the semiconductor encapsulation material is a cast product or a molded product.
• the compound is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further cured by heating at 80 to 230 ° C. for 0.5 to 10 hours. You can get things.
• the cured product of the varnish for a circuit board is a laminated product.
• a circuit board varnish is impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and dried by heating to obtain a prepreg, which is used alone. It can be obtained by laminating with a metal foil such as copper foil and hot press molding.
• the curable resin composition of the present invention can be used by laminating with a metal foil (meaning including a metal plate; the same applies hereinafter) as in the case of the cured composite material described later.
• a substrate is added to the curable composite material according to the curable resin composition of the present invention in order to increase mechanical strength and dimensional stability.
• Examples of such a base material include various glass cloths such as roving cloths, cloths, chopped mats and surfaced mats, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths, all aromatic polyamide fibers, and all.
• Woven or non-woven fabrics obtained from liquid crystal fibers such as aromatic polyester fibers and polybenzozar fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers and acrylic fibers, cotton cloth, linen cloth, felt and the like.
• Examples thereof include cloths such as fiber cloths, carbon fiber cloths, kraft papers, cotton papers, natural cellulose-based cloths such as paper-glass mixed fiber papers, and papers. Each of these may be used alone or two or more kinds may be used.
• the proportion of the base material in the curable composite material is preferably 5 to 90% by mass, preferably 10 to 80% by mass, and more preferably 20 to 70% by mass.
• a coupling agent can be used, if necessary, for the purpose of improving the adhesiveness at the interface between the resin and the base material.
• 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.
• the curable resin composition of the present invention and other components, if necessary, are placed in the above-mentioned aromatic, ketone or the like solvent or a mixed solvent thereof.
• the substrate is uniformly dissolved or dispersed, impregnated into a substrate, 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.
• a cured composite material can be obtained by curing the curable composite material of the present invention by a method such as heating.
• the manufacturing method is not particularly limited, and for example, a plurality of curable composite materials are laminated, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. be able to. It is also possible to obtain a composite material cured product having a new layer structure by combining the cured composite material once adhesively cured and the curable composite material. Laminate molding and curing are usually performed at the same time using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by laminating and molding in advance can be cured by heat treatment or another method.
• Molding and curing are performed at a temperature of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm 2 , a time of 1 minute to 10 hours, more preferably a temperature of 150 to 250 ° C., a pressure of 1 to 500 kg / cm 2 , and a time of 1. It can be done in the range of minutes to 5 hours.
• the laminate of the present invention is composed of a layer of a cured composite material of the present invention and a layer of a metal foil.
• the metal foil used here include copper foil and aluminum foil.
• the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 3 to 105 ⁇ m.
• a curable resin composition for example, a curable resin composition, a curable composite material obtained from a substrate, and a metal leaf are laminated in a layer structure according to the purpose, and each layer is subjected to heating and pressurization. There is a method of heat-curing at the same time as adhering the resin.
• the cured composite material and the metal foil are laminated in an arbitrary layer structure.
• the metal leaf can be used as both a surface layer and an intermediate layer.
• Adhesive can also be used for adhesion to metal foil.
• the adhesive include, but are not limited to, epoxy-based, acrylic-based, phenol-based, cyanoacrylate-based, and the like. Laminate molding and curing can be performed under the same conditions as in the production of the cured composite material of the present invention.
• the curable resin composition of the present invention can also be molded into a film.
• the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 5 to 105 ⁇ m.
• the method for producing the film of the present invention is not particularly limited, and for example, the curable resin composition and, if necessary, other components are uniformly mixed in a solvent such as an aromatic or ketone solvent or a mixed solvent thereof. Examples thereof include a method of dissolving or dispersing in a resin, applying it to a resin film such as a PET film, and then drying it.
• the coating can be repeated multiple times as needed, and at this time, the coating can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust the desired resin composition and amount. Is.
• the resin-containing metal leaf of the present invention is composed of the curable resin composition of the present invention and the metal leaf.
• the metal foil used here include copper foil and aluminum foil.
• the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 5 to 105 ⁇ m.
• the method for producing the metal leaf with resin of the present invention is not particularly limited, and for example, the curable resin composition and, if necessary, other components are mixed with a solvent such as an aromatic or ketone solvent or a mixed solvent thereof.
• a solvent such as an aromatic or ketone solvent or a mixed solvent thereof.
• examples thereof include a method in which the solvent is uniformly dissolved or dispersed therein, applied to a metal foil, and then dried.
• the coating can be repeated multiple times as needed, and at this time, the coating 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.
• Dielectric constant and dielectric loss tangent Evaluated by obtaining the dielectric constant and dielectric loss tangent at a frequency of 1 GHz by the capacitive method using a material analyzer (manufactured by Agilent Technologies) according to IPC-TM-650 2.5.5.9. did.
• Thermal conductivity was measured by the transient hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.
• Synthesis example 1 200 parts of 1-naphthol was charged into a reaction device equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a dropping funnel, and heated to 110 ° C. to dissolve while introducing nitrogen. Then, 0.19 parts of p-toluenesulfonic acid was added, the temperature was raised to 130 ° C. with stirring, 70 parts of p-xylylene glycol dimethyl ether was added dropwise from the dropping funnel over 3 hours, and another 1.5 parts of p-. -Toluenesulfonic acid was added, and it was confirmed that there was no heat generation, and 61 parts of p-xylylene glycol dimethyl ether was added dropwise and reacted for 5 hours.
• Synthesis example 2 A reactor equipped with a stirrer, a cooling tube, and a nitrogen introduction tube is charged with 500 parts of P4, 30 parts of methanol, and 2.5 parts of p-toluenesulfonic acid, heated while introducing nitrogen, and 100 parts while stirring. The temperature was raised at ° C. and the reaction was carried out for 5 hours. Then, after removing p-toluenesulfonic acid by washing with water, the temperature was raised to 200 ° C. under reduced pressure to remove unreacted methanol, and 505 parts of phenol resin (P2) was obtained. The hydroxyl group equivalent of the obtained P2 was 254, and the methoxy denaturation rate was 16 mol%.
• Example 1 A reaction device equipped with a temperature controller, a stirrer, and a cooling condenser was prepared, and 301 parts of P1, 159 parts of V1, and 702 parts of diethylene glycol dimethyl ether were charged, and the mixture was stirred and dissolved to bring the liquid temperature to 75 ° C. After 0.92 parts of tetra-n-butylammonium bromide was charged, 61.7 parts of potassium hydroxide was added in 8 portions so that the reaction time was 7 hours. After confirming the consumption of V1 by gas chromatography, 0.42 parts of trimethylhydroquinone was added, diethylene glycol dimethyl ether was distilled, and then 987 parts of toluene was added and redissolved.
• the obtained curable resin composition varnish is applied to a PET film, dried in an oven at 130 ° C. for 5 minutes, crushed into powder, filled in a mold, and vacuumed at 210 ° C. and 2 MPa for 1 hour. A pressure press was performed and thermosetting was performed to obtain a cured product having a thickness of 2 mm. The Tg, dielectric constant, dielectric loss tangent, and thermal conductivity of the obtained cured product were measured. The measurement results are shown in Table 1.
• Example 2 to 3 Comparative Examples 1 to 5
• the same operation as in Example 1 was carried out according to the charged amount (part) of each raw material shown in Table 1, and the poly (vinylbenzyl) ether compound (resins R2 to R3, RH1 to 5), the curable resin composition varnish, and the curing were carried out. I got something.
• the same measurements as in Example 1 were performed, and the results are shown in Table 1.
• Ether compounds provide a cured product with a high glass transition point, low dielectric tangent, and high thermal conductivity, and have been shown to be useful in applications typified by electrical and electronic materials.
• the poly (vinylbenzyl) ether compound of the present invention is useful for applications such as electric / electronic materials, laminated materials, molding materials, and casting materials.

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• 2021
  • 2021-11-05 JP JP2022563694A patent/JPWO2022107624A1/ja active Pending
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