JP2005314556A - Poly(vinylbenzyl) ether compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material having high heat-resistance, low water-absorption and low dielectric constant. <P>SOLUTION: The poly(vinylbenzyl) ether compound is expressed by formula (1) (R<SB>1</SB>groups are each independently hydrogen atom, a 1-6C alkyl, allyl or an aryl; R<SB>2</SB>groups are each independently hydrogen atom or vinylbenzyl group wherein the substitution ratio of hydrogen atom to the vinylbenzyl group is 20-100%; n is 1-10 on an average; and m is 1-4). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to insulating materials for electrical and electronic parts including those for highly reliable semiconductor sealing, and various composite materials such as laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastics), or molding raw materials. The present invention relates to a poly (vinylbenzyl) ether compound useful as a compound, a production method thereof, a composition containing the poly (vinylbenzyl) ether compound, and a cured product thereof.

  Conventionally, curable resins are widely used for adhesion, casting, coating, impregnation, lamination, molding compound, and the like. However, in recent years, there are various uses, and depending on the use environment and use conditions, conventionally known curable resins may not be able to cope with them. For example, in a laminated board used for various electric devices, high performance such as high heat resistance and low water absorption is required with the recent progress of electronic devices. In particular, a curable resin excellent in electrical characteristics such as a low dielectric constant and a low dielectric loss tangent has been demanded from demands such as high computation speed of computers, high propagation speed, and high frequency of mobile communication devices.

  Currently, the matrix resin of the laminated board that is mainly put into practical use includes phenol aralkyl resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, polyimide resin, etc., but these resins have high heat resistance, Although demands such as low water absorption have been met (Patent Documents 1 to 3), low dielectric constant and low dielectric loss tangent are not sufficiently satisfied. As a solution to such a problem, vinyl benzyl ether compounds are described in Patent Documents 4 to 6, but the dielectric properties of the cured products described in these Patent Documents have the performance currently required. It is not fully achieved.

JP-A-5-117350 (page 1-6) JP-A-8-143648 (pages 1-17) JP2003-113225A (page 1-5) JP 63-68537 A (page 1-6) Japanese Patent Laid-Open No. 5-43623 (pages 1-7) US Pat. No. 4,116,936 (pages 1-8)

  The present invention provides a cured product exhibiting heat resistance, low water absorption, and low dielectric constant, insulating materials for electrical and electronic parts including those for highly reliable semiconductor encapsulation, and laminates (printed wiring boards) and CFRP ( Poly (vinyl benzyl) ether compound useful for various composite materials such as carbon fiber reinforced plastic) or as a raw material for molding, its production method, composition containing the poly (vinyl benzyl) ether compound and its It aims at providing hardened | cured material.

  As a result of intensive studies to develop a curable resin having the above-mentioned properties, the present inventor has found that a poly (vinylbenzyl) ether compound having a specific structure solves the above-mentioned problems. Was completed.

That is, the present invention provides (1) the following general formula (1)

（式（１）中、Ｒ_１はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、アリル基、またはアリール基を、Ｒ_２はそれぞれ独立して水素原子またはビニルベンジル基をそれぞれ示す（但し、水素原子のビニルベンジル基への置換率は２０〜１００％である。）。ｎは平均値で１〜１０を、ｍは１〜４の数を示す。）で表されるポリ（ビニルベンジル）エーテル化合物、
（２）一般式（１）で表されるポリ（ビニルベンジル）エーテル化合物において、Ｒ_１が水素原子であり、Ｒ_２が４−ビニルベンジル基および３−ビニルベンジル基からなる群から選ばれる少なくとも１種である（１）に記載のポリ（ビニルベンジル）エーテル化合物、
（３）下記一般式（２）

(In formula (1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and R ₂ each independently represents a hydrogen atom or a vinylbenzyl group. (However, the substitution rate of the hydrogen atom to the vinylbenzyl group is 20 to 100%.) N is an average value of 1 to 10, and m is a number of 1 to 4.) Vinylbenzyl) ether compound,
(2) In the poly (vinylbenzyl) ether compound represented by the general formula (1), at least R ₁ is a hydrogen atom, and R ₂ is selected from the group consisting of a 4-vinylbenzyl group and a 3-vinylbenzyl group. The poly (vinylbenzyl) ether compound according to (1), which is one kind,
(3) The following general formula (2)

（式（２）中、Ｒ_１はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、アリル基、またはアリール基を示し、ｍは１〜４の数を示す。）で表されるフェノール類と下記一般式（３）

(In Formula (2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and m represents a number of 1 to 4). Phenols and the following general formula (3)

（式（３）中、Ｘは活性基を表す。）で表されるビフェニル化合物とを縮合して得られるフェノールアラルキル樹脂とビニルベンジルハライドとをアルカリ金属水酸化物の存在下で反応させて得られる、ポリ（ビニルベンジル）エーテル化合物、
（４）下記一般式（２）

(In formula (3), X represents an active group) Obtained by reacting a phenol aralkyl resin obtained by condensing a biphenyl compound represented by the formula (II) with vinylbenzyl halide in the presence of an alkali metal hydroxide. A poly (vinylbenzyl) ether compound,
(4) The following general formula (2)

（式（２）中、Ｒ_１はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、アリル基、またはアリール基を示し、ｍは１〜４の数を示す。）で表されるフェノール類と下記一般式（３）

(In Formula (2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and m represents a number of 1 to 4). Phenols and the following general formula (3)

（式（３）中、Ｘは活性基を表す。）で表されるビフェニル化合物とを縮合して得られるフェノールアラルキル樹脂とビニルベンジルハライドとをアルカリ金属水酸化物の存在下で反応させることを特徴とする、ポリ（ビニルベンジル）エーテル化合物の製造方法、
（５）フェノールアラルキル樹脂とビニルベンジルハライドとの反応において相間移動触媒を用いることを特徴とする（４）に記載のポリ（ビニルベンジル）エーテル化合物の製造方法、
（６）一般式（２）で表されるフェノール類においてＲ_１が水素原子であり、ビニルベンジルハライドが、４−ビニルベンジルクロライドおよび３−ビニルベンジルクロライドからなる群から選ばれる少なくとも１種である（４）又は（５）のいずれか一項に記載のポリ（ビニルベンジル）エーテル化合物の製造方法、
（７）（１）又は（２）のいずれか一項に記載のポリ（ビニルベンジル）エーテル化合物を含有する硬化性樹脂組成物、
（８）（７）に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。

(In formula (3), X represents an active group) a phenol aralkyl resin obtained by condensing a biphenyl compound represented by the formula (3) and vinylbenzyl halide are reacted in the presence of an alkali metal hydroxide. A method for producing a poly (vinylbenzyl) ether compound,
(5) A method for producing a poly (vinylbenzyl) ether compound according to (4), wherein a phase transfer catalyst is used in the reaction between the phenol aralkyl resin and vinylbenzyl halide,
(6) In the phenols represented by the general formula (2), R ₁ is a hydrogen atom, and the vinylbenzyl halide is at least one selected from the group consisting of 4-vinylbenzyl chloride and 3-vinylbenzyl chloride. (4) or the method for producing a poly (vinylbenzyl) ether compound according to any one of (5),
(7) A curable resin composition containing the poly (vinylbenzyl) ether compound according to any one of (1) or (2),
(8) A cured product obtained by curing the curable resin composition according to (7),
About.

  The poly (vinyl benzyl) ether compound of the present invention gives a cured product excellent in heat resistance, moisture resistance and dielectric properties as compared with conventional vinyl benzyl ether compounds. Therefore, the poly (vinyl benzyl) 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 has the general formula (2)

(In formula (2), R ₁ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and m represents a number of 1 to 4). And the following general formula (3)

(In the above formula (3), X represents an active group) and a biphenyl compound represented by the following general formula (4) is condensed.

(In the formula (4), R ₁ and m have the same meaning as in the general formula (2), and n represents an average value of 1 to 10) and a phenol aralkyl resin represented by vinyl benzyl halide. It can be obtained by reacting in the presence of an alkali metal hydroxide.

  The phenol represented by the general formula (2) is a compound having at least one phenolic hydroxyl group on the benzene ring, and is an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group. Has ~ 4 substituents. Examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group; isopropyl group, sec -Branched alkyl groups such as butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; cyclic alkyl such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl Is mentioned. Examples of the aryl group include a phenyl group and a naphthyl group. In the present invention, the phenol is preferably phenol.

  In the general formula (3), X is an active group, such as a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group. Specific examples of the general formula (3) include, for example, 4,4′-bis (fluoromethyl) -1,1′-biphenyl, 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 etc. are mentioned. In the present invention, 4,4'-bis (chloromethyl) -1,1'-biphenyl is preferred.

  The phenol aralkyl resin represented by the general formula (4) is, for example, as described in Patent Document 1 to Patent Document 3, after a phenol and a biphenyl compound are subjected to a condensation reaction, unreacted phenols And by removing impurities.

  In the production method of the present invention, the amount of the phenol represented by the general formula (2) to the biphenyl compound represented by the general formula (3) is 1 mol of the biphenyl compound represented by the general formula (3). It is 1.1-10 mol normally with respect to it, Preferably it is 1.5-7.0 mol.

  In the production method of the present invention, an acid catalyst can be used as necessary in the condensation reaction between the biphenyl compound represented by the general formula (3) and the phenols represented by the general formula (2). Examples of the acid catalyst include organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid and oxalic acid; Friedel-Crafts type catalysts such as stannic chloride, zinc chloride and ferric chloride. Is not limited. Of these, sulfuric acid, p-toluenesulfonic acid, and stannic chloride are preferable, but p-toluenesulfonic acid is particularly preferable in the production method of the present invention. Although the usage-amount of these acid catalysts changes with kinds of catalyst, it is preferable to use in the range of 0.0005-10 weight% with respect to the biphenyl compound represented by the said General formula (3).

  In the production method of the present invention, the reaction temperature in the condensation reaction between the biphenyl compound represented by the general formula (3) and the phenol represented by the general formula (2) 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 performed while charging all the raw materials at once, or may be performed by sequentially adding the biphenyl compound while maintaining the phenols at a constant temperature. The reaction can be carried out without solvent, but organic compounds such as toluene, monochlorobenzene, dichlorobenzene, or lower alcohols such as methanol, ethanol, propanol, and butanol, which are not directly involved in the reaction, can also be used as a solvent.

  The hydrochloric acid gas generated during the reaction may be removed from the system by flowing an inert gas such as nitrogen gas, or may be removed under reduced pressure.

  After completion of the reaction, impurities such as hydrogen chloride and acid catalyst generated during the reaction are neutralized and removed by washing with water. Then, the phenol aralkyl resin represented by the general formula (4) can be obtained by recovering unreacted phenols and solvent. In the general formula (4), the average value n is preferably 1 to 10 as measured by gel permeation chromatography (GPC). The recovery of unreacted phenols and solvent is preferably distilled off under normal pressure or reduced pressure. It is also possible to blow off water vapor and distill it off with water vapor distillation. The temperature for phenol recovery by distillation is 100 to 180 ° C., and the degree of vacuum is preferably about 0.1 to 25 kPa.

  In the production method of the present invention, the reaction between the obtained phenol aralkyl resin and vinyl benzyl halide is not particularly limited. For example, the phenol aralkyl resin and vinyl benzyl halide are dehalogenated from an alkali metal hydroxide. The poly (vinylbenzyl) ether compound of the present invention can be obtained by using it as a hydrogenation agent.

  Examples of the vinyl benzyl halide include 4-vinyl benzyl chloride, 3-vinyl benzyl chloride, a mixture of 4-vinyl benzyl chloride and 3-vinyl benzyl chloride, 4-vinyl benzyl bromide, 3-vinyl benzyl bromide, 4 -The mixture etc. of vinyl benzyl bromide and 3-vinyl benzyl bromide are mentioned. Among these, at least one selected from the group consisting of 4-vinylbenzyl chloride and 3-vinylbenzyl chloride is preferable. When 4-vinylbenzyl chloride is used, structural symmetry is improved, and a poly (vinylbenzyl) ether compound that gives a cured product having a high melting point and a high softening point can be obtained. Further, when a mixture of 4-vinylbenzyl chloride and 3-vinylbenzyl chloride is used, the poly (vinylbenzyl) ether compound of the present invention which gives a cured product having a low melting point and a low softening point and good workability is obtained. be able to.

  The reaction between the phenol aralkyl resin and the vinyl benzyl halide includes, for example, adding an alkali metal hydroxide solid such as potassium hydroxide, sodium hydroxide and a mixture thereof to the mixture of the phenol aralkyl resin and the vinyl benzyl halide, or The reaction is carried out at 30 to 100 ° C. for 0.5 to 20 hours while adding. At this time, the alkali metal hydroxide may be used as an aqueous solution, and in this case, the alkali metal hydroxide can be continuously added. The amount of alkali metal hydroxide used is usually 0.6 to 2.0 mol, preferably about 0.9 to 1.7 mol, per mol of phenolic hydroxyl group of the phenol aralkyl resin.

  In the production method of the present invention, the amount of vinylbenzyl halide used can be adjusted as appropriate, but it is preferably 0.4 to 1.20 mol per mol of the phenolic hydroxyl group of the phenol aralkyl resin. At this time, in order to increase the solubility of the phenol aralkyl resin and vinyl benzyl halide, it is preferable to carry out the reaction by adding a polar neutral solvent.

  Examples of the polar neutral solvent include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, and tetramethylene sulfone. , Hexamethylphosphoamide, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like, but are not limited thereto. These may be used alone or in combination of two or more. The amount of the polar neutral solvent used is preferably 5 to 800% by weight based on the weight of the phenol aralkyl resin.

  In addition, the poly (vinylbenzyl) ether compound of the present invention can also be obtained by the method for producing a vinylbenzyl ether compound of the present invention in which a phase transfer catalyst is added to a mixture of a phenol aralkyl resin and a vinylbenzyl halide. As the phase transfer catalyst, for example, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetra-n-butylammonium bromide, and the like can be used. The amount of the salt used is usually 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of the phenol aralkyl resin hydroxyl group.

  In addition, in the manufacturing method of this invention, the substitution rate to the vinylbenzyl group of the phenolic hydroxyl group of General formula (2) can be suitably adjusted with the usage-amount of vinylbenzyl halide. In the poly (vinylbenzyl) ether compound of the present invention, the substitution rate of the hydrogen atom of the phenolic hydroxyl group to the vinylbenzyl group is 10 to 100%, preferably 20 to 100%. This substitution rate is preferably as high as possible from the viewpoint of dielectric properties such as low dielectric constant and low dielectric loss tangent of the cured product of the present invention, but is appropriately adjusted when used in combination with other thermosetting resins. The

  When it is necessary to completely remove the intermediate phenol aralkyl resin in the production method of the present invention, reprecipitation purification by adjusting the amount of vinylbenzyl halide used or other means, for example, a solvent / non-solvent system combination What is necessary is just to remove an unreacted raw material etc. by a method.

  Hereinafter, the curable resin composition of the present invention will be described. In the curable resin composition of the present invention, the poly (vinylbenzyl) ether compound of the present invention can be used alone or in combination with a compound copolymerizable with the poly (vinylbenzyl) ether compound.

Examples of the compound that can be used together with the poly (vinylbenzyl) ether compound of the present invention and copolymerizable with the poly (vinylbenzyl) ether compound include styrene, vinyltoluene, divinylbenzene, divinylbenzyl ether, allylphenol, allyloxy, and the like. Examples thereof include, but are not limited to, benzene, diallyl phthalate, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone and the like. These may be used alone or in combination of two or more. The compounding ratio of these compounds is about 2 to 50% by weight with respect to the poly (vinylbenzyl) ether compound.

  Further, examples of the compound that is used in combination with the poly (vinylbenzyl) ether compound of the present invention and that can be copolymerized with the poly (vinylbenzyl) ether compound include further known thermosetting resins such as vinyl ester resins and unsaturated polyesters. Examples thereof include resins, maleimide resins, polyphenol polycyanate resins, epoxy resins, phenol aralkyl resins, vinyl benzyl compounds, and known thermoplastic resins such as polyether imide, polyether sulfone, polyacetal, and dicyclopentadiene resins. Among these, vinyl ester resins, unsaturated polyester resins, maleimide resins, polyphenol polycyanate resins, and epoxy resins are preferable, and these may be used alone or in combination of two or more. The blending ratio is about 5 to 90% by weight with respect to the poly (vinylbenzyl) ether compound of the present invention.

  The curable resin composition of the present invention may contain a curing agent. As the curing agent, known radical polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl perbenzoate can be used. In the curable resin composition of the present invention, the amount of the curing agent used is 0 to 10 with respect to 100 parts by weight of the compound copolymerizable with the poly (vinylbenzyl) ether compound that can be used in combination with the poly (vinylbenzyl) ether compound. Parts by weight.

  Moreover, hydroquinone, benzoquinone, copper salt, etc. can be mix | blended as a stabilizer for adjustment of a hardening degree.

  Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol, triethylenediamine, Tertiary amines such as triethanolamine and 1,8-diazabicyclo (5,4,0) undecene-7; organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine; metal compounds such as tin octylate; Tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate; 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmol Tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like. When the curing accelerator is used, the amount used is 0.01 to 15 parts by weight with respect to 100 parts by weight of the compound copolymerizable with the poly (vinylbenzyl) ether compound that can be used in combination with the poly (vinylbenzyl) ether compound. Is used as needed.

  Furthermore, the curable resin composition of the present invention includes various fillers such as an inorganic filler, a silane coupling agent, a stabilizer, a release agent, and a pigment as required, various thermosetting resins and thermoplastic resins, Reinforcing fibers can be added.

  Examples of the inorganic filler include silica, alumina, zirconia, titanium dioxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, diatomaceous earth, mica, potassium titanate whisker, lithium titanate whisker, and zinc oxide whisker. However, it is not limited to these. These may be used alone or in combination of two or more.

  Examples of the reinforcing fibers include, but are not limited to, fibers such as glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, and alumina fibers. These may be used alone or in combination of two or more.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above components. The polymerization and curing of the curable resin composition of the present invention can be performed by a known method. Curing can be performed in the presence or absence of a curing agent. If necessary, for example, a curing accelerator and an inorganic filler, a compounding agent, various thermosetting resins / thermoplastic resins, reinforcing fibers, If necessary, thoroughly mix until uniform using an extruder, kneader, blender, roll, etc. to obtain the curable resin composition of the present invention, and the curable resin composition is melt cast or Molded by transfer molding method, injection molding method, compression molding method, etc., and the curing temperature varies depending on whether or not the curing agent is used and the type of curing agent, but cannot be defined unconditionally, but is 20 to 250 ° C, preferably 50 The cured product of the present invention can be obtained by heating at 250 ° C. for 2 to 10 hours. If the temperature is less than 20 ° C., sufficient curing cannot be obtained.

  Further, a glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, which is a reinforcing fiber obtained by dissolving the curable resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, A cured product of the present invention can also be obtained by hot press molding a prepreg obtained by impregnating a substrate such as alumina fiber and drying by heating.

  In addition, when the curable resin composition of the present invention is impregnated in a substrate such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber, which is a reinforcing fiber, it is molded by filament winding and heated. By doing so, the cured product of the present invention can also be obtained.

  Moreover, what melt | dissolved the curable resin composition of this invention in solvents, such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, can be used also as a varnish, a coating material, and an adhesive agent.

  The amount of the solvent used in this case is usually 5 to 90% by weight, preferably 10 to 80% by weight, of the total weight of the curable resin composition of the present invention and the solvent.

Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “part” in the examples means “part by weight” and “%” means “% by weight”. The number of n in the poly (vinylbenzyl) ether compound represented by the general formula (1) and the phenol aralkyl resin represented by the general formula (2) is determined by gel permeation chromatography (column: GPC KF-803 + KF-802.5 + KF). −802 + KF-801 (manufactured by Showa Denko); column temperature: 40 ° C .; eluent: tetrahydrofuran; flow rate: 1 ml / min; detection: RI). Moreover, the method of the various measurements performed in the Example is described below.
Measurement of softening point: Measured according to JIS K7234 Infrared absorption spectrum: Fourier transform infrared spectrophotometer FTIR-8400 made by Shimadzu Rika Instruments

Example 1
While purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge, 414 parts of phenol, 251 parts of 4,4′-bis (chloromethyl) -1,1′-biphenyl, p-toluenesulfonic acid 13 The portion was charged and heated up to 80 ° C. with stirring to be dissolved. After stirring for 4 hours, 700 parts of methyl isobutyl ketone was added and then washed three times with 300 parts of water until the washing water became neutral. Then, unreacted phenol and methyl isobutyl ketone were removed from the oil layer under a pressure of 1.3 kPa. In general formula (4), 310 parts of phenol aralkyl resin (P) in which R ₁ is a hydrogen atom and n is 1.5 were obtained. The obtained phenol aralkyl resin had a softening point of 65 ° C. and a hydroxyl group equivalent of 202 g / eq.

While purging a flask equipped with a thermometer, condenser, and stirrer with nitrogen gas purge, 404 parts of the obtained phenol aralkyl resin (P), 848 parts of methyl ethyl ketone, 320 parts of 4-vinylbenzyl chloride, tetra n-butyl 12 parts of ammonium bromide was added and dissolved by stirring to bring the liquid temperature to 70 ° C. Thereto, 320 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and stirring was further continued at 70 ° C. for 6 hours. Next, after neutralizing the flask contents with 35% hydrochloric acid, liquid separation was performed, and the organic layer was washed three times with 400 parts of water, and unreacted raw materials and methyl ethyl ketone were distilled off under reduced pressure. , R ₁ is a hydrogen atom, R ₂ is a vinylbenzyl group, and n is 1.5, to obtain 512 parts of the poly (vinylbenzyl) ether compound (VB1) of the present invention. The resulting poly (vinylbenzyl) ether compound had a softening point of 54 ° C., and as a result of infrared absorption spectrum measurement, absorption due to the phenolic hydroxyl group of the raw material disappeared.

Example 2
404 parts of phenol aralkyl resin (P) obtained by synthesizing in the same manner as in Example 1 while performing nitrogen gas purging on a flask equipped with a thermometer, a condenser, and a stirrer, 848 parts of methyl ethyl ketone, 3-vinylbenzyl 96 parts of chloride, 224 parts of 4-vinylbenzyl chloride and 12 parts of tetra-n-butylammonium bromide were charged and dissolved by stirring, and the liquid temperature was adjusted to 70 ° C. Thereto, 320 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and stirring was further continued at 70 ° C. for 6 hours. Next, after neutralizing the flask contents with 35% hydrochloric acid, liquid separation was performed, and the organic layer was washed three times with 400 parts of water, and unreacted raw materials and methyl ethyl ketone were distilled off under reduced pressure. , 509 parts of the poly (vinylbenzyl) ether compound (VB2) of the present invention in which R ₁ is a hydrogen atom, R ₂ is a vinylbenzyl group, and n is 1.5. The resulting poly (vinylbenzyl) ether compound had a softening point of 52 ° C., and as a result of infrared absorption spectrum measurement, absorption due to the phenolic hydroxyl group of the raw material disappeared.

Synthesis example 1
While purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas, 348 parts of phenol resin (Mirex XL-225-3L, Mitsui Chemicals, hydroxyl equivalent 174 g / eq), 731 parts of methyl ethyl ketone, 4- 320 parts of vinylbenzyl chloride and 11 parts of tetra-n-butylammonium bromide were charged, dissolved by stirring, and the liquid temperature was adjusted to 70 ° C. Thereto, 320 parts of 30% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and stirring was further continued at 70 ° C. for 6 hours. Next, after neutralizing the contents of the flask with 35% hydrochloric acid, liquid separation was performed, and the organic layer was washed with 400 parts of water three times, and methyl ethyl ketone and the like were distilled off under reduced pressure. As a result, 494 parts of a poly (vinylbenzyl) ether compound (VB3) equivalent to the above example was obtained.

Examples 3 and 4, Comparative Example 1
The poly (vinylbenzyl) ether compound (VB1 · VB2) of the present invention obtained in Examples 1 and 2 and the poly (vinylbenzyl) ether compound (VB3) obtained in Synthesis Example 1 as a comparative example were obtained at 130 ° C. Cured for 5 hours at 230 ° C. to obtain the cured products of the present invention (Examples 3 and 4) and the cured product of Comparative Example 1; test specimens were prepared; glass transition temperature (TMA); water absorption rate; Tests were conducted on the rate items under the following conditions, and the test results are shown in Table 1.

Comparative Example 2
198 parts of an o-cresol novolak type epoxy resin (EOCN-1020, manufactured by Nippon Kayaku) as an epoxy resin, 106 parts of a phenol novolak (softening point 83 ° C., hydroxyl group equivalent 106 g / eq) as a curing agent, and triphenylphosphine as a curing accelerator (Pure Chemical (manufactured)) 2 parts are mixed while heating, transfer molded at 175 ° C. for 180 seconds, then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to obtain the cured product of Comparative Example 2. A test piece was prepared and tested for glass transition temperature (TMA), water absorption, and dielectric constant under the following conditions. The test results are shown in Table 1.

Glass transition temperature Thermomechanical measurement device (TMA): Vacuum Riko TM-7000
Temperature increase rate: 2 ° C./min.
-Water absorption rate Test piece: Disk of diameter 5 cm x thickness 4 mm Weight increase (% by weight) after boiling for 24 hours in warm water at 100 ° C
-Dielectric constant Measured according to JIS K-6911

Table 1
Example 3 Example 4 Comparative Example 1 Comparative Example 2
Sample VB1 VB2 VB3 EOCN-1020
Physical properties of cured product Glass transition point (° C.) 255 251 245 161
Water absorption rate (%) 0.4 0.4 0.5 1.2
Dielectric constant (1 MHz) 2.8 2.8 3.0 4.0

  As is clear from the comparison of the test results of Examples 3 and 4 above, the poly (vinylbenzyl) ether compound of the present invention obtained by using only 4-vinylbenzyl halide as the vinylbenzyl halide (Example 3: VB1). Has a glass transition point as compared with the poly (vinylbenzyl) ether compound of the present invention (Example 4: VB2) obtained using a mixture of 3-vinylbenzyl halide and 4-vinylbenzyl halide as vinylbenzyl halide. A high cured product was obtained. In addition, the poly (vinylbenzyl) ether compound of the present invention gives a cured product having a high glass transition point, a low water absorption, and a low dielectric constant compared to conventional phenol resins and epoxy resins, and is representative of electrical and electronic materials. It has been shown to be useful for certain applications.

Claims (8)

The following general formula (1)

(In formula (1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and R ₂ each independently represents a hydrogen atom or a vinylbenzyl group. (However, the substitution rate of the hydrogen atom to the vinylbenzyl group is 20 to 100%.) N is an average value of 1 to 10, and m is a number of 1 to 4.) Vinyl benzyl) ether compound. In the poly (vinylbenzyl) ether compound represented by the general formula (1), R ₁ is a hydrogen atom, and R ₂ is at least one selected from the group consisting of a 4-vinylbenzyl group and a 3-vinylbenzyl group. The poly (vinylbenzyl) ether compound according to claim 1. The following general formula (2)

(In Formula (2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and m represents a number of 1 to 4). Phenols and the following general formula (3)

(In formula (3), X represents an active group) Obtained by reacting a phenol aralkyl resin obtained by condensing a biphenyl compound represented by the formula (II) with vinylbenzyl halide in the presence of an alkali metal hydroxide. A poly (vinylbenzyl) ether compound. The following general formula (2)

(In Formula (2), each R ₁ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group, and m represents a number of 1 to 4). Phenols and the following general formula (3)

(In formula (3), X represents an active group) a phenol aralkyl resin obtained by condensing a biphenyl compound represented by the formula (3) and vinylbenzyl halide are reacted in the presence of an alkali metal hydroxide. A method for producing a poly (vinylbenzyl) ether compound, which is characterized. The method for producing a poly (vinylbenzyl) ether compound according to claim 4, wherein a phase transfer catalyst is used in the reaction between the phenol aralkyl resin and vinylbenzyl halide. 5. The phenol represented by the general formula (2), wherein R ₁ is a hydrogen atom, and the vinyl benzyl halide is at least one selected from the group consisting of 4-vinyl benzyl chloride and 3-vinyl benzyl chloride. Or the manufacturing method of the poly (vinyl benzyl) ether compound as described in any one of Claim 5. A curable resin composition comprising the poly (vinylbenzyl) ether compound according to claim 1. A cured product obtained by curing the curable resin composition according to claim 7.