JP3414556B2 - Polyvinyl benzyl ether compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyvinyl benzyl ether compound and a method for producing the same, and more specifically, the present invention is good and constant over a wide frequency range and depends on temperature and hygroscopicity. TECHNICAL FIELD The present invention relates to a polyvinyl benzyl ether compound that exhibits difficult dielectric properties and is also excellent in heat resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, curable resins have been widely used for bonding, casting, coating, impregnating, laminating and molding compounds. However, in recent years, its applications have been diversified, and there are cases where conventionally known curable resins cannot be satisfied depending on the use environment and use conditions.

For example, a laminated board used for various electric devices is required to have high performance with the progress of electronic devices in recent years. In particular, materials with a low dielectric constant and a low dielectric loss tangent are required in order to meet the demands for high computer computing speed, high propagation speed, and high frequency for mobile communication devices, etc. It is also required to be independent of gender.

At present, the matrix resin of the laminated board which is mainly used includes phenol resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, polyimide resin and the like. These resins have a low dielectric constant, It does not sufficiently satisfy the low dielectric loss tangent, and its dielectric properties also tend to depend on temperature and hygroscopicity. Although the polyimide resin has high heat resistance, its dielectric property tends to depend on hygroscopicity.

In order to solve the above problems, Japanese Patent Laid-Open No. 63-6
In Japanese Patent No. 8537 and Japanese Patent Laid-Open No. 64-65110, polymers of vinylbenzyl compounds having improved dielectric properties are disclosed, and dielectric properties after boiling water absorption of a cured product have been reported. The dependence of dielectric properties is not yet sufficient. Further, in these conventional techniques, the dependence of the dielectric properties on temperature has not been clarified.

In addition to this, various polymers having a vinylbenzyl group have been proposed. For example, Japanese Patent Laid-Open No. 1-13
No. 2616, No. 1-204922, No. 2-88609, No. 2-110120, No. 2-134340, No. 3-203.
No. 12, JP-A-4-164904, and JP-A-4
-164909, Japanese Patent Laid-Open No. 4-31409,
The compounds described in JP-A-4-31410, JP-A-4-31411, JP-A-4-31412 and the like are exemplified, but the electrical characteristics including the dielectric characteristics are still insufficient. Further, these prior arts do not disclose or suggest the polyvinyl benzyl ether compound of the present invention at all.

[0007]

Therefore, the present invention is
It is an object of the present invention to provide a polyvinyl benzyl ether compound which exhibits good and constant dielectric properties in a wide frequency range, is hard to depend on temperature and hygroscopicity, and is also excellent in heat resistance, and a method for producing the same.

[0008]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides the following general formula (1)

[0009]

[Chemical 8]

(Wherein R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a hydrogen atom or a vinylbenzyl group (provided that The molar ratio of hydrogen atom to vinylbenzyl group is 6
0:40 to 0: 100), and n represents a number of 2 to 4).

The present invention also relates to the following general formula (2)

[0012]

[Chemical 9]

(In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 2 to 4) And a vinylbenzyl halide in the presence of an alkali metal hydroxide to provide a polyvinylbenzyl ether compound represented by the above general formula (1).

Further in the present invention, the vinylbenzyl halide is at least one selected from the group consisting of p-vinylbenzyl chloride and m-vinylbenzyl chloride.
The above-mentioned polyvinyl benzyl ether compound, which is a seed, is provided.

Furthermore, the present invention is characterized in that the polyphenol represented by the above general formula (2) is reacted with vinylbenzyl halide in the presence of an alkali metal hydroxide to produce a polyvinylbenzyl ether compound. It provides a method.

The present invention also provides the above-mentioned production method wherein the reaction is carried out in the presence of a phase transfer catalyst.

Further, the present invention provides a curable resin composition containing a polyvinyl benzyl ether compound represented by the above general formula (1) and a monomer copolymerizable therewith.

Furthermore, the present invention comprises the group consisting of the polyvinylbenzyl ether compound represented by the above general formula (1), a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a polycyanate resin of polyphenol, an epoxide resin and a mixture thereof. The present invention provides a curable resin composition containing at least one thermosetting resin selected from

The present invention further comprises the polyvinyl benzyl ether compound represented by the following general formula (1) itself, or the polyvinyl benzyl ether compound and a monomer or a thermosetting resin copolymerizable therewith. The present invention provides a cured resin obtained by curing the curable resin composition as described above.

The present invention will be described in more detail below. In the polyvinyl benzyl ether compound of the present invention represented by the above general formula (1), R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a benzyl group. R ³ represents a hydrogen atom or a vinylbenzyl group. Here, the molar ratio of hydrogen atom to vinylbenzyl group is 60: 40-
It is 0: 100. Also, n has a value of 2 to 4. The polyvinyl benzyl ether compound of the general formula (1) of the present invention comprises a polyphenol represented by the above general formula (2),
It can be synthesized by reacting with vinylbenzyl halide.

As the polyphenol of the general formula (2), commercially available products can be used, for example, PP-700-300 and PP-1000-180 manufactured by Nippon Petrochemical Co., Ltd.
Etc.

The vinylbenzyl halides include p-vinylbenzyl chloride, m-vinylbenzyl chloride, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide and p. Examples include a mixture of -vinylbenzyl bromide and m-vinylbenzyl bromide. Among them, p-vinylbenzyl chloride and a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride are preferable. When p-vinylbenzyl chloride is used, the symmetry is improved, and a polyvinyl benzyl ether compound having a high melting point and a high softening point can be obtained. Further, when a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride is used, a polyvinyl benzyl ether compound having a low melting point and a low softening point is obtained, and workability is improved.

The reaction between the polyphenol and the vinylbenzyl halide is not particularly limited, but for example, the polyphenol and the vinylbenzyl halide are reacted in a polar neutral solvent using an alkali metal hydroxide as a dehydrochlorinating agent. There is a method.

The mixing ratio of polyphenol and vinylbenzyl halide can be appropriately designed, but for example, the molar ratio can be polyphenol: vinylbenzyl halide = 100: 40 to 100: 120.

As the polar neutral solvent, dimethylformamide, dimethylsulfoxide, dimethylacetamide,
N-methylpyrrolidone, dioxane, acetonitrile,
Tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone, hexamethylphosphoamide, methyl ethyl ketone, methyl isobutyl ketone, acetone and mixtures thereof.

Examples of alkali metal hydroxides include potassium hydroxide, sodium hydroxide and mixtures thereof. The mixing ratio of the alkali metal hydroxide is preferably about 1.1 to 2.0 times mol per mol of the phenolic hydroxyl group.

The reaction temperature and the reaction time are 30 and 30, respectively.
It may be 0.5 to 20 hours at -100 ° C.

As another method, a phase transfer catalyst,
For example, in the presence of a quaternary ammonium salt, the above polyphenol and vinylbenzyl halide are mixed in a water / organic solvent mixed solution with an alkali metal hydroxide as a dehydrochlorinating agent to form 100
The polyvinylbenzyl ether compound of the present invention can be obtained by reacting at a temperature up to ° C.

When the polyvinyl benzyl ether compound of the present invention is produced by the above-mentioned method, the phenolic hydroxyl group in the polyphenol of the general formula (2), which is one of the starting materials, is changed by the blending design of polyphenol and vinylbenzyl halide. It is possible to make one that is not entirely substituted with vinylbenzyl groups. In this case, the product obtained by the above reaction is a mixture of the polyvinyl benzyl ether compound of the present invention and the polyphenol of the general formula (2). In the present invention, the polyphenol may be present as long as it is less than the specific ratio, that is, less than 60 mol% with respect to both. However, if it exceeds 60 mol%, the curing reaction to be carried out later is not sufficiently achieved, and good dielectric properties are not exhibited, which is not preferable.

The substitution ratio of the polyphenol hydroxyl group of the general formula (2) to the vinylbenzyl group is 40 to 100 mol%, preferably 60 to 100 mol%. As a matter of course, the higher the substitution rate, the more desirable. This substitution rate can be appropriately adjusted by designing the composition of polyphenol and vinylbenzyl halide.

When the presence of polyphenols is not allowed, unreacted raw materials and the like may be removed by designing the composition of polyphenols and vinylbenzyl halide and appropriate means, for example, a reprecipitation purification method using a solvent / non-solvent system combination.

The polyvinyl benzyl ether compound of the present invention, when polymerized and cured with itself or another copolymerizable monomer, is good and constant in a wide frequency range, and is hardly dependent on temperature and hygroscopicity. It can be used as a resin that exhibits dielectric properties and is also excellent in heat resistance.

Examples of the copolymerizable monomer include styrene, vinyltoluene, divinylbenzene, divinylbenzyl ether, allylphenol, allyloxybenzene, diallylphthalate, acrylic acid ester, methacrylic acid ester and vinylpyrrolidone. .
The mixing ratio of these monomers is about 2 to 50% by weight with respect to the polyvinyl benzyl ether compound.

The polyvinyl benzyl ether compound of the present invention is a known thermosetting resin such as vinyl ester resin, unsaturated polyester resin, maleimide resin, polyphenol polycyanate resin, epoxy resin, phenol resin, vinyl benzyl compound and the like. It is also possible to use it in combination with a known thermoplastic resin such as polyetherimide, polyethersulfone, polyacetal, dicyclopentadiene resin and the like. The blending ratio is about 5 to 90% by weight with respect to the polyvinyl benzyl ether compound of the present invention. Among them, preferably
It is at least one selected from the group consisting of vinyl ester resins, unsaturated polyester resins, maleimide resins, polyphenol polycyanate resins, epoxide resins and mixtures thereof.

Polymerization and curing of the polyvinyl benzyl ether compound of the present invention itself or a curable resin composition containing the compound and another monomer or a thermosetting resin can be carried out by a known method. it can. Curing can be in the presence or absence of a curing agent. When a curing agent is used, for example, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t
-A known radical polymerization initiator such as butyl perbenzoate can be used. The amount used is 0 to 10 parts by weight based on 100 parts by weight of the polyvinyl benzyl ether compound.

The curing temperature varies depending on whether or not the curing agent is used and the type of the curing agent, and therefore cannot be specified unconditionally, but it is 20 to 250 ° C., preferably 50 to 250 ° C. If the temperature is lower than 20 ° C, sufficient curing cannot be obtained.

Needless to say, hydroquinone, benzoquinone, copper salt, etc. may be added for the purpose of adjusting the curing.

The polyvinyl benzyl ether compound of the present invention can be made into a molding material or a composite material by blending various other fillers and reinforcing fibers with a kneader, blender, roll or the like, if necessary. Examples of fillers include
Silica, alumina, zirconia, titanium dioxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate,
Examples thereof include diatomaceous earth, mica, potassium titanate whiskers, barium titanate whiskers, and zinc oxide whiskers. Examples of the reinforcing fiber include single fiber such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber and alumina fiber. Also useful as a varnish, paint or adhesive by dissolving it in a solvent, and as a prepreg by impregnating reinforcing fibers such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber or alumina fiber, or as filament winding. It can be a material or a structural material.

[0039]

EXAMPLES The present invention will be described below with reference to examples. In addition, unless otherwise indicated, the part in an example means a weight part. The methods of various measurements performed in the examples are described below. Measurement of softening point: According to JIS K7234. Thermogravimetric analysis: Rigaku differential thermal balance TG-DTA THERMOFLEX
Using TG8110, 5% weight loss temperature in air was measured at a heating rate of 10 ° C / min. Glass transition temperature (Tg): Oriento RHEOVIBR
The ON MODEL DDV-25FP was used, and the DMA method was performed under the condition of a vibration frequency of 11 Hz. Infrared absorption spectrum: Measured using a Fourier transform infrared spectrophotometer JIR-RFX3002FT-IR SPECTROPHOTOMETER manufactured by JEOL Ltd. ¹ H nuclear magnetic resonance spectrum: measured using JNM-PMX60SI manufactured by JEOL Ltd. using tetramethylsilane as an internal standard substance. Liquid chromatography: THF was used as an eluent, and Shodex GPCKF 801 manufactured by Showa Denko KK was used as a column. Differential Refraction: Measured using RI SE-51 manufactured by Showa Denko KK. Residual phenol group: Measured by the neutralization titration method of JIS K0070. Dielectric property: LCR made by Yokogawa Hewlett-Packard Company with dielectric constant and dielectric loss tangent in the range of 100 Hz to 30 MHz.
It was measured by the balanced bridge method using meters 4285A and 4285B. However, the dielectric loss tangent of 5 MHz or more was measured by the resonance method.

Example 1 A 1-liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel was used as PP-700-300 manufactured by Nippon Petrochemical Co., Ltd. as a polyphenol corresponding to the general formula (2). 79.3 g (0.25 eq),
As vinylbenzyl halide, 42.7 g (0.28 equivalent) of vinylbenzyl chloride CMS-AM (m- / p-isomer: 30/70% by weight mixture) manufactured by Seimi Chemical Co., tetra-n-butylammonium bromide 2.4.
g, 2,4-dinitrophenol 0.038 g and methyl ethyl ketone 200 g were charged and dissolved with stirring to a liquid temperature of 75.
℃, and sodium hydroxide aqueous solution (sodium hydroxide 2
0 g (0.5 equivalent) / 20 g of water) was added dropwise over 20 minutes,
Further, stirring was continued at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with a 10% aqueous hydrochloric acid solution, toluene 100
g was added, the organic layer was washed 3 times with 300 ml of water, methyl ethyl ketone and toluene were removed under reduced pressure, and the reaction product was precipitated in 300 ml of methanol.
Polyvinyl benzyl ether compound of the present invention having a softening point of 87 ° C. (PP-700-300-100VB,
The same applies hereinafter). This PP-700-300-100
In the general formula (1), VB has R ¹ as a methyl group, R ² as a benzyl group, and n as 3.

The product was confirmed by liquid chromatography (LC analysis), infrared absorption spectrum (IR) and ¹ H nuclear magnetic resonance spectrum (NMR). From LC analysis, no unreacted vinylbenzyl chloride is present, no phenolic hydroxyl group is present from IR, N
By confirming a signal showing a vinylbenzyl group at around 5 to 6 ppm by MR, it was confirmed that the obtained product was a vinylbenzyl ether compound having a structure represented by the general formula (1). PP-700-300- in FIG.
The IR chart of 100VB is shown. Also JIS K0
By measuring the hydroxyl equivalent weight by the neutralization titration method of 070, the phenolic hydroxyl group is absent (the molar ratio of the hydrogen atom of R ³ in the general formula (1) to the vinylbenzyl group is 0:10).
It was also confirmed that 0).

In addition, PP-700-300-100VB
Was melted at 120 ° C., poured into a glass plate to a thickness of 2 mm, thermally polymerized at 120 ° C. for 2 hours, and after-cured at 150 ° C. for 2 hours and 180 ° C. for 2 hours to obtain PP. Table 1 shows the results of thermogravimetric analysis (temperature showing 5% weight loss in air) and Tg measurement results of the -700-300-100VB cured product.

Furthermore, this cured product having a thickness of 2 mm is 5 cm × 5
Cut out to a size of cm, 100Hz ~ 30 of this test piece
Dielectric constant and dielectric loss tangent in the MHz range were measured. The results are shown in Table 2. Also, this test piece is placed in boiling water for 48 hours.
After boiling for a period of time, the water absorption rate (dry weight / percentage of weight after water absorption) was measured, and the dielectric constant and dielectric loss tangent were measured again.
The results are shown in Table 3.

Example 2 PP-700-300 manufactured by Nippon Petrochemical Co., Ltd. was used as a polyphenol corresponding to the general formula (2) in a 1-liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel. 79.3 g (0.25 eq),
As vinylbenzyl halide, 36.2 g (0.238 equivalent) of vinylbenzyl chloride CMS-AM (m- / p-isomer: 30/70% by weight mixture) manufactured by Seimi Chemical Co., tetra-n-butylammonium bromide 2.4.
g, 2,4-dinitrophenol 0.038 g and methyl ethyl ketone 200 g were charged and dissolved with stirring to a liquid temperature of 75.
℃, and sodium hydroxide aqueous solution (sodium hydroxide 2
0 g (0.5 equivalent) / 20 g of water) was added dropwise over 20 minutes,
Further, stirring was continued at 75 ° C. for 4 hours. Next, the contents of the flask were neutralized with a 10% aqueous hydrochloric acid solution, and then separated, and the organic layer was washed 3 times with 300 ml of water, and methyl ethyl ketone was removed under reduced pressure to obtain PP- having a softening point of 87 ° C. at a yield of 95%. 700-
300-95 VB was obtained. This PP-700-300-
95VB is a compound represented by the general formula (1), wherein R ¹ is a methyl group,
R ² is a benzyl group and n is 3.

The product was confirmed by LC analysis and NMR. From the LC analysis, it was confirmed that no unreacted vinylbenzyl chloride was present, and from NMR, a signal showing a vinylbenzyl group was confirmed at around 5 to 6 ppm, whereby the obtained product had the structure represented by the general formula (1). Is a vinyl benzyl ether compound of phenol,
Further, the hydroxyl equivalent was measured by the neutralization titration method of JIS K0070, and 5 mol% of phenolic hydroxyl groups were present (the molar ratio of hydrogen atom of R ³ to vinylbenzyl group in the general formula (1) was 5:95). It was confirmed.

Further, the same operation as in Example 1 was carried out.
Curing was performed at 0-300-95VB, and thermogravimetric analysis results and Tg measurement of the cured product were performed. The results are shown in Table 1.

Furthermore, PP-700-300-95VB
Was melted at 120 ° C., poured into a glass plate so as to have a thickness of 1 mm, thermally polymerized at 120 ° C. for 2 hours, and then after-cured at 150 ° C. for 2 hours and 180 ° C. for 2 hours. This 1 mm thick cured product is 1 cm x 1 cm
Cut out to a size of × 1 mm, and the test piece of −50 ° C.
100Hz, 1KHz, 10K in the range of 200 ° C
The dielectric constant and dielectric loss tangent of each frequency of Hz, 100 KHz, and 1 MHz were measured. The results are shown in Tables 5 to 9.

Example 3 In the same operation as in Example 2, vinylbenzyl chloride was reacted with polyphenol to give 80 mol% of phenolic hydroxyl groups to vinylbenzyl groups (hydrogen atom of R ³ in the general formula (1) and vinylbenzyl group). The molar ratio of the groups is 20:
80), 60 mol% (the molar ratio of the hydrogen atom of R ³ in the general formula (1) to the vinylbenzyl group is 40:60) and 40 mol% (the hydrogen atom of R ³ in the general formula (1) and the vinylbenzyl group). At a molar ratio of 60:40), and PP-700-300-80VB (softening point 88 ° C.) and PP-700-300-60VB (softening point 1 respectively).
12 ° C) and PP-700-300-40VB (softening point 125 ° C) were obtained. The confirmation of the compound was also performed in the same manner as in Example 2. Fig. 2 shows the IR of PP-700-300-80VB
Shows a chart of.

As in Example 1, PP-700-300
The dielectric constant and dielectric loss tangent of -80VB and PP-700-300-60VB were measured. In addition, PP-700-
For 300-80VB, the water absorption, and the dielectric constant and dielectric loss tangent after water absorption were measured in the same manner as in Example 1.
The results are shown in Tables 2 to 4.

Comparative Example 1 45 g of a dicyclopentadiene skeleton phenol resin DPP-3H (manufactured by Nippon Petrochemical Co., Ltd.) was placed in a 1-liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel. 0.25 equivalent), vinylbenzyl chloride CMS-AM (m- / p-isomer: 30
/ 70 wt% mixture, Seimi Chemical Co., Ltd.) 38.
1 g (0.25 equivalent), tetra-n-butylammonium bromide 2.4 g, 2,4-dinitrophenol 0.0
38 g and 200 g of methyl ethyl ketone were charged and dissolved with stirring, and an aqueous solution of sodium hydroxide (20 g of sodium hydroxide (0.5 equivalents) / 20 g of water) was added at 20 ° C. to 20 wt.
The mixture was added dropwise over 1 minute, and stirring was continued at 75 ° C for 4 hours. Next, the contents of the flask were neutralized with hydrochloric acid and then separated, and the organic layer was washed three times with 300 ml of water, and methyl ethyl ketone was removed under reduced pressure to obtain DPP-3H-100VB at a yield of 95%. The product is confirmed by liquid chromatography (LC analysis), I
It was confirmed by R and NMR that no unreacted vinylbenzyl chloride was present, no phenolic hydroxyl group was present, and that it was a vinylbenzyl ether compound of a dicyclopentadiene skeleton phenol resin.

Furthermore, 12 DPP-3H-100VB
Melt at 0 ° C, pour between glass plates to a thickness of 1 mm, heat-polymerize at 120 ° C for 2 hours, then
After-curing was performed at 50 ° C. for 2 hours and 180 ° C. for 2 hours. This 1 mm thick cured product is 1 cm x 1 cm x 1 m
Cut out to a size of m, -50 ℃ ~ 200 of this test piece
100Hz, 1KHz, 10KHz in the range of ℃,
The dielectric constant and dielectric loss tangent at each frequency of 100 KHz and 1 MHz were measured. The results are shown in Tables 5 to 9.

Comparative Example 2 To 100 parts of epoxy resin Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd.), 2 parts of 2-ethyl-4-methylimidazole (produced by Shikoku Kasei Co., Ltd.) were added, and the thickness was 2 m.
It is poured between glass plates so as to have a thickness of m, cured at 80 ° C. for 2 hours, and after-cured at 150 ° C. for 2 hours, and a 2 mm thick cured product is cut into a size of 5 cm × 5 cm to obtain a test piece (828). -2E4MZ), and the dielectric constant and dielectric loss tangent were measured as in Example 1. The results are shown in Table 3.
And shown in Table 4. The water absorption of this test piece was measured in the same manner as in Example 1, and the dielectric constant and dielectric loss tangent after water absorption were also measured. The results are also shown in Tables 3 and 4.

Comparative Example 3 Vinyl ester resin Lipoxy RF-313 (manufactured by Showa Highpolymer Co., Ltd.) 100 parts, perhexa 3M (1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 1 part of Nippon Oil & Fats Co., Ltd. was added and poured into a glass plate so that the thickness would be 2 mm, followed by curing at 80 ° C. for 2 hours and after-curing at 120 ° C. for 2 hours. Was cut into a size of 5 cm × 5 cm to obtain a test piece (RF-313), and the dielectric constant and the dielectric loss tangent were measured in the same manner as in Example 1. The results are shown in Table 3.
And shown in Table 4. The water absorption of this test piece was measured in the same manner as in Example 1, and the dielectric constant and dielectric loss tangent after water absorption were also measured. The results are also shown in Tables 3 and 4.

Comparative Example 4 Epoxy resin Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd.) 100 parts, methylhymic acid (produced by Hitachi Chemical Co., Ltd.) 81 parts and DMP-30 (2,4,6-tris) (Dimethylaminomethyl) phenol (manufactured by Seiko Kagaku Co., Ltd.) (1 part) was added, and the mixture was poured into a glass plate so as to have a thickness of 1 mm. After curing at 100 ° C. for 5 hours, 15
After-curing was performed at 0 ° C for 15 hours to obtain a test piece (828-MNA) in the same manner as in Example 2, -50 ° C to 200 ° C.
The dielectric constant and the dielectric loss tangent in the range were measured. The results are shown in Tables 5 to 9.

Example 4 PP-700-300-100VB synthesized in Example 1
100 parts of the mixture was melted at 120 ° C, and 15 parts of styrene monomer (SM) was melted and poured into a glass plate so as to have a thickness of 2 mm, followed by thermal polymerization at 120 ° C for 2 hours, and then at 150 ° C for 2 hours. And after-curing at 180 ° C. for 2 hours. This 2mm thick cured product is 5cm x
It was cut into a size of 5 cm, and the dielectric constant and the dielectric loss tangent in the range of 100 Hz to 30 MHz were measured by the same operation as in Example 1. The measurement results are shown in Table 10. Also, this 5cm × 5cm
A 2 mm test piece was boiled in boiling water for 48 hours to measure the water absorption, and then the dielectric constant and dielectric loss tangent were measured in the same manner as in Example 1. The results are also shown in Table 10.

Example 5 PP-700-300-100VB synthesized in Example 1
100 parts of the mixture was melted at 120 ° C., and a mixture of 30 parts of diphenylmethane bismaleimide (BMI, manufactured by Mitsui Toatsu Co., Ltd.) was poured into a glass plate so as to have a thickness of 2 mm, and heat-polymerized at 120 ° C. for 2 hours. After that, 150 ℃
After curing for 2 hours at 180 ° C. for 2 hours and at 200 ° C. for 2 hours, Tg was measured. Also, this 2mm
Cut a thick cured product into a size of 5 cm x 5 cm, and cut for 100H
The dielectric constant and the dielectric loss tangent in the range of z to 30 MHz are set in Example 1.
It measured by the same operation as. The measurement results are shown in Table 11.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

[0066]

[Table 10]

[0067]

[Table 11]

From the results shown in Table 1, it is understood that the polyvinyl benzyl ether compound of the present invention has excellent heat resistance. Further, the results in Table 2 show that the polyvinyl benzyl ether compound of the present invention has good and constant dielectric properties in a wide frequency range. Furthermore, from the results of Table 3 and Table 4, the polyvinyl benzyl ether compound of the present invention is
Compared with the compound of Comparative Example, it shows a dielectric property that does not change much even after absorbing water in a wide frequency range. Furthermore, from the results of Tables 5 to 9, it is understood that the polyvinyl benzyl ether compound of the present invention exhibits a constant and excellent dielectric property over a wide range of frequencies and over a wide range of temperatures, as compared with the compounds of Comparative Examples. Further, from the results of Table 10 and Table 11, a cured product of a composition comprising the polyvinyl benzyl ether compound of the present invention and a monomer copolymerizable therewith,
It can be seen that the cured product of the composition comprising the polyvinyl benzyl ether compound and the thermosetting resin has good dielectric properties in a wide frequency range.

[0069]

Industrial Applicability According to the present invention, a polyvinyl benzyl ether compound which exhibits good and constant dielectric properties in a wide frequency range, is hardly dependent on temperature and hygroscopicity, and is excellent in heat resistance, and a method for producing the same are provided. To be done.

[Brief description of drawings]

FIG. 1 PP-700-300-1 obtained in Example 1
It is a figure which shows the result of IR analysis of 00VB.

FIG. 2 PP-700-300-8 obtained in Example 3
It is a figure which shows the result of IR analysis of 0VB.

Continuation of the front page (56) Reference JP-A-7-196768 (JP, A) JP-A-6-211964 (JP, A) JP-A-7-10962 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C07C 43/00 C07C 39/00 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. The following general formula (1): (In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³
Represents a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0:
100) and n represents a number of 2 to 4). 2. The following general formula (2): (Wherein R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 2 to 4), and vinyl. Benzyl halide is reacted in the presence of an alkali metal hydroxide to obtain the following general formula (1): (In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³
Represents a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0:
100) and n represents a number of 2 to 4). 3. The polyvinylbenzyl ether compound according to claim 2, wherein the vinylbenzyl halide is at least one selected from the group consisting of p-vinylbenzyl chloride and m-vinylbenzyl chloride. 4. The following general formula (2): (Wherein R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 2 to 4), and vinyl. A method for producing a polyvinyl benzyl ether compound, which comprises reacting with a benzyl halide in the presence of an alkali metal hydroxide. 5. The method for producing a polyvinyl benzyl ether compound according to claim 4, wherein the reaction is carried out in the presence of a phase transfer catalyst. 6. The method for producing a polyvinylbenzyl ether compound according to claim 4, wherein the vinylbenzyl halide is at least one selected from the group consisting of p-vinylbenzyl chloride and m-vinylbenzyl chloride. 7. The following general formula (1): (In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³
Represents a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0:
100), and n represents a number of 2 to 4), and a curable resin composition comprising a monomer copolymerizable therewith. 8. The following general formula (1): (In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³
Represents a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0:
100)), n represents a number of 2 to 4), and a group consisting of a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a polyphenol polycyanate resin, an epoxide resin, and a mixture thereof. A curable resin composition containing at least one thermosetting resin selected from the group consisting of: 9. The following general formula (1): (In the formula, R ¹ represents a methyl group or an ethyl group, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ³
Represents a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0:
100), and n represents a number of 2 to 4), or the polyvinyl benzyl ether compound itself, or the polyvinyl benzyl ether compound and a monomer or a thermosetting resin copolymerizable therewith. A cured resin obtained by curing the curable resin composition as described above.