JPH0834832A - Thermosetting resin composition and copper-clad laminate - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition excellent in dielectric properties by mixing a compound prepared by previously reacting an epoxy resin with a halogenated bisphenol compound with a polyisocyanate compound and an epoxy curing agent. CONSTITUTION:This composition is one essentially consisting of a compound prepared by previously reacting an epoxy resin represented by formula I with a halogenated bisphenol compound represented by formula II, a polyisocyanate compound having at least two cyanate groups in the molecule and an epoxy curing agent and having a content of the polycyanate compound of 5-50wt.%. In the formula, n is the average number of repeating units and is 0-10; R1 is H or a 1-9C alkyl; P is at least a 4-9C alkyl or the like, is 1-3; R2 is H or methyl; X and X' are each a halogen; k and l are each 1-4; R3 is H or the like; Q and Q' are each a 1-9 C alkyl or the like; and j and m are each 0-4.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition and a copper-clad laminate, and more particularly to a thermosetting resin composition having excellent dielectric properties and a copper-clad laminate.

[0002]

2. Description of the Related Art Among epoxy resins used for electric and electronic purposes, a combination of a bisphenol type epoxy resin and dicyandiamide has been mainly used as a material for a printed wiring board (copper-clad laminate). recent years,
With the increase in the number of layers of printed wiring boards, low dielectric constant and low dielectric loss tangent of resin have been required mainly for the purpose of improving signal speed and reducing transmission loss. On the other hand, a method of combining a conventional epoxy resin with a thermoplastic resin having a low dielectric constant and a low dielectric loss tangent has been devised. For example, a method of modifying with a reactive polybutadiene resin, a method of dispersing powder of polytetrafluoroethylene resin, and the like. In addition, a laminated board using an imide resin or a cyanate resin, which has better dielectric properties than an epoxy resin, is also used.

[0003]

However, in these conventional techniques, since the basic epoxy resin has a high dielectric constant and a high dielectric loss tangent, the proportion of the thermoplastic resin to be combined becomes large in order to achieve the desired dielectric properties. However, the heat resistance, dimensional stability, chemical resistance, etc., which are the characteristics of epoxy resin, are impaired. In addition, although the imide resin and the cyanate resin have high heat resistance and excellent dielectric properties, they have the drawbacks of high cost and high manufacturing cost because they require high temperature and long time for heat molding. Therefore, there has been a strong demand for a thermosetting resin having excellent dielectric properties such that a printed circuit board having a low dielectric constant and a low dielectric loss tangent can be obtained by the completely same method as the conventional method.
An object of the present invention is to provide a thermosetting resin composition which gives a cured product having excellent dielectric properties (both the dielectric constant and the dielectric loss tangent are low) and a copper clad laminate molded using the thermosetting resin composition.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted diligent research on a combination of an epoxy resin, a cyanate compound and an epoxy curing agent. As a result, an epoxy resin, a cyanate compound and an epoxy curing agent having a skeleton having excellent dielectric properties have been obtained. It was found that a thermosetting resin composition in combination with an agent satisfies the above-mentioned object, and has completed the present invention. That is, the present invention comprises the inventions described below. (1) (A) General formula (1)

[0005]

[Chemical 4] (In the formula, n represents an average number of repetitions and takes a value of 0 or more and 10 or less. R ₁ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. P independently represents at least one carbon atom. An alkyl group having 4 to 9 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, the other is an alkyl group having 1 to 9 carbon atoms, and i is independently an integer value of 1 or more and 3 or less. . If i is 2 or more, P
May be the same or different in the same ring. ) And an epoxy resin (B) represented by the general formula (2)

[0006]

Embedded image (In the formula, R ₂ represents a hydrogen atom or a methyl group, and two R ₂ may be the same or different.
X and X ′ are halogen atoms, and they may be the same or different from each other. k and l are 1 independently
It is an integer not less than 4 and not more than 4. ) And a compound obtained by previously reacting with a halogen-containing bisphenol compound represented by
(2) Thermosetting resin composition in which a polycyanate compound having two or more cyanate groups in the molecule and (3) an epoxy curing agent are essential components, and the content of the polycyanate compound is 5 to 50% by weight. The present invention relates to an epoxy resin copper-clad laminate obtained by heating and molding a prepreg obtained by dissolving the composition in an organic solvent and impregnating the base material with a copper foil. The present invention will be described in detail below. The epoxy resin as the component (A) used in the present invention has the general formula (4)

[0007]

[Chemical 6] (In the formula, R ₁ , P, and i are defined in the same manner as in the case of the general formula (1).) And obtained by glycidyl etherification of the polyphenol compound.

The polyphenol compound represented by the general formula (4) is produced by a commonly used method for producing a novolac type phenolic resin. Examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, or benzenesulfonic acid, toluenesulfonic acid, It is produced by polycondensation of phenols and aldehydes using an organic acid such as oxalic acid or a metal salt such as zinc acetate as a catalyst.

The phenols include n-butylphenol, isobutylphenol, t-butylphenol,
Various alkylphenols represented by octylphenol, nonylphenol, methylbutylphenol, di-t-butylphenol, di-t-amylphenol, etc.
Examples are o-, m-, p-isomers, and various o-, m-, p-isomers of cycloalkylphenol typified by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol and the like. Alternatively, they may be used as a mixture of two or more kinds. Among these phenols, 2-t-butyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-t-butylphenol, 2- sec-butylphenol, 4-t-butylphenol, 4-sec-butylphenol, 2- (t-amyl) phenol, 4-
Examples thereof include (t-amyl) phenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 4-t-octylphenol, 4-nonylphenol and the like.
Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
Examples thereof include alkyl aldehydes such as pentyl aldehyde.

Glycidyl etherification of the polyphenol compound represented by the general formula (4) is carried out by a known method. For example, it can be carried out by reacting this polyphenol compound with epichlorohydrin in the presence of an alkali such as caustic soda. In the general formula (1), the average number of repeating units n is 0 to 10, preferably 0.
-5, more preferably 0-3. When the number of repeating units exceeds 10, the viscosity as an epoxy resin increases,
There is a drawback in that workability in producing a laminated plate is reduced.

Specific examples of the halogen-containing bisphenol compound represented by the general formula (2) of the component (B) used in the present invention include tetrabromobisphenol A, tetrachlorobisphenol A, tetraiodobisphenol A, Tetrabromobisphenol F, tetrachlorobisphenol F, tribromobisphenol A, 2,
Although 2'-dibromobisphenol A and the like can be mentioned, tetrabromobisphenol A is preferably used from the viewpoint of economical efficiency and imparting efficient flame retardancy.

The reaction between the epoxy resin (A) and the halogen-containing bisphenol compound (B) can be carried out by a known method. For example, the above components can be reacted in the presence of a basic catalyst such as triphenylphosphine or imidazole. By reacting, it is possible to control the glass transition temperature by changing the distance between cross-linking points and impart flame retardancy using a halogen-containing compound without volatilization of low molecular weight substances during curing. The components (A) and (B) can be reacted at any ratio. Epoxy resin (A)
Is 30 to 90% by weight of the whole resin to maintain the dielectric properties.
It is preferable to use in the range of. The halogen-containing bisphenol compound (B) is preferably used in a proportion such that the quantitative proportion of the halogen atoms contained in the halogen-containing bisphenol compound (B) can achieve V-0 in the UL standard flame retardancy evaluation of the laminate. For example, in the case of a bromine atom, the bromine atom is 1
It is desirable to determine the use ratio of these components so as to be contained in an amount of 0 to 25% by weight, and it is desirable to similarly prepare when other bromine-containing compounds are used in combination.

The reaction of the above components may be carried out with or without a solvent. When using a solvent, a general-purpose organic solvent can be used. Examples thereof include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as tetrahydrofuran, dioxane and diethylene glycol dimethyl ether, alcohol solvents such as methyl cellosolve and butyl cellosolve. Examples of the solvent include methyl ethyl ketone, toluene, xylene, butyl cellosolve, dioxane, and diethylene glycol dimethyl ether. The reaction temperature of the above components can be carried out within the range of 50 to 200 ° C, but it is preferably carried out within the range of 80 to 150 ° C in order to carry out the reaction efficiently and suppress side reactions. The polycyanate compound used in the present invention is a compound having two or more cyanate groups in the molecule, for example, the compound represented by the general formula (3)

[0014]

[Chemical 7] (In the formula, R ₃ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and two R ₃ may be the same or different. Q and Q ′ are alkyl groups having 1 to 9 carbon atoms,
It represents a cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, which may be the same or different. j and m are independently 0 or more and 4
It is the following integer. ) Is a compound represented by. These compounds are obtained by reaction of the corresponding polyphenol compounds with cyanogen halides. This reaction is known and is described, for example, in US Pat. 3,755,402 and 4,028,
393 Described in the specification. Further, among the polycyanate compounds, 2,2-bis (4-cyanatophenyl) propane and bis (4-cyanate-3,5-5-acetic acid) are more preferable for lowering the dielectric constant and lowering the dielectric loss tangent.
Dimethylphenyl) methane, 1,1-bis (4-cyanatophenyl) cyclohexane, 1,1-bis (4-cyanato-3-methylphenyl) cyclohexane, 1,
Examples thereof include 1-bis (5-t-butyl-4-cyanato-2-methylphenyl) butane, but are not limited thereto. The blending amount thereof is 5 to 50% by weight, preferably 10 to 30% by weight, based on the whole resin composition. If the content is less than 5% by weight, lowering of the dielectric constant and lowering of the dielectric loss tangent cannot be achieved.

As the epoxy resin curing agent used in the present invention, known curing agents can be used. For example, phenol novolac, cresol novolac, 1,1,
1-Trishydroxyphenylethane, polycondensates of phenols with aromatic aldehydes, oligomers of adducts of phenols with unsaturated alicyclic compounds, polybutadiene compounds modified with phenols, xylylene-bonded oligomers of phenols Examples thereof include polyhydric phenols such as polyhydroxystyrene and polyhydroxybromostyrene, amine curing agents such as aromatic amines and aliphatic amines, acid anhydrides, dicyandiamide, hydrazide compounds, and Lewis acid complexes. Preferred are polybutadiene compounds modified with phenols, dicyandiamide or polyhydric phenols. Further, the blending amount thereof is preferably 0.3 to 1.2 equivalents with respect to the epoxy groups in the epoxy resin.

Further, to the extent that the effects of the present invention are not impaired,
Conventionally known bifunctional epoxy resin, polyfunctional epoxy resin,
It is also possible to use another thermosetting resin or a thermoplastic resin having a functional group in combination. Specifically, glycidyl ether of bisphenol A, glycidyl ether of tetrabromobisphenol A, glycidyl ether of phenol novolac, glycidyl ether of cresol novolac, glycidyl ether of brominated phenol novolac, unsaturated polyester resin, maleimide resin, glycidyl modified polybutadiene. , Maleic anhydride-modified polyethylene and the like. These resins can be used by mixing them in the epoxy resin composition used in the present invention or by pre-reacting with the epoxy resin used in the present invention.

In the present invention, known additives such as a curing accelerator, a flame retardant and a surface treatment agent may be added to the composition depending on the purpose. Imidazoles, tertiary amines, phosphorus compounds, organic metal salts, Lewis acids and the like as curing accelerators, antimony trioxide, aluminum hydroxide, red phosphorus and the like as flame retardants, and silane cup as a surface treatment agent. Examples thereof include ring agents, and these may be used alone or as a mixture of two or more kinds.

The copper-clad laminate of the present invention can be prepared by a known method. That is, a base material is impregnated with a resin varnish obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent, and a heat treatment is performed to form a prepreg, and then the prepreg and the copper foil are laminated and heat-formed to form a copper-clad laminate. Is the way. The organic solvent used is selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, N, N-dimethylformamide, dioxane, tetrahydrofuran and the like, or a mixture of two or more thereof. It

The base material to be impregnated with the resin varnish is a woven cloth, a non-woven cloth, a mat, a paper or the like made of inorganic fibers such as glass fibers and organic fibers such as polyester fibers and polyamide fibers, which are used alone or in combination. To be The heat treatment conditions for the prepreg are appropriately selected depending on the solvent used, the catalyst added, and the types and amounts of various additives used, but are usually at a temperature of 80 ° C. to 220 ° C. for 3 minutes to 30 minutes. Heat molding conditions are exemplified 20 to 300 minutes of thermal press molding at a molding pressure of 10kg / cm ² ~100kg / cm ² at a temperature of 0.99 ° C. to 300 ° C..

[0020]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In the examples, the epoxy equivalent is defined as the molecular weight of the epoxy resin per epoxy group. The OH equivalent is defined as the molecular weight of the OH compound per one OH group. The Br content is defined as wt% based on resin solids. Synthesis Example 1 This synthesis example relates to a production example of a novolac resin which is a raw material of the epoxy resin (A) which is a constituent component of the resin composition of the present invention. 2-t-butyl-5-methylphenol 2231.0 g (13.58 mol), p-toluenesulfonic acid 12.
9 g (0.068 mol) and 223.2 g of ion-exchanged water are charged into a 5 liter four-neck round bottom flask equipped with a thermometer, a stirrer and a condenser, and heated to 100 ° C. Formaldehyde 218.
After 4 g (2.715 mol) was added dropwise using a dropping tube over 2 hours, the mixture was kept at 100 ° C. for 2 hours to carry out a novolak reaction. After that, it was cooled to 80 ° C and 27.7 g (0.0
It was neutralized with 69 mol). The organic layer after liquid separation was washed twice with 700 g of ion-exchanged water. The organic layer after washing is concentrated under reduced pressure (180 ° C / 1
(0 mmHg / 1 hour) to obtain 857.2 g of a resinous material. The OH equivalent of the obtained resinous material was 176.0 g / eq. The average number of repeating units (n in the general formula (4)) of this novolac resin was 1.25.

Synthesis Example 2 This synthesis example relates to a production example in which an epoxy resin is obtained by reacting the novolak resin of Synthesis Example 1 with epichlorohydrin. 246.4 g (1.4%) of the novolak resin of Synthesis Example 1
OHmol), 906.5 g (9.8 mol) of epichlorohydrin, 453.3 g of dimethyl sulfoxide, and 14.0 g of ion-exchanged water are charged into a 2 liter 4-neck round bottom flask equipped with a thermometer, a stirrer, and a condenser with a separation tube. 108.31 g (1.316 mol) of 48.6% aqueous sodium hydroxide solution was added dropwise under the condition of 49 ° C. and 42 torr over 5 hours. During this time, while keeping the temperature at 49 ° C., the azeotropic epichlorohydrin and water were cooled and liquefied, and the reaction was performed while returning the organic layer into the reaction system. After the reaction was completed, unreacted epichlorohydrin was removed by concentration under reduced pressure, the epoxidized product containing a byproduct salt and dimethylsulfoxide was dissolved in methyl isobutyl ketone, and the byproduct salt and dimethylsulfoxide were removed by washing with warm water. The solvent was removed under reduced pressure to obtain 304.9 g of epoxy resin. The epoxy equivalent of the epoxy resin thus obtained was 256 g / eq. As a result of infrared absorption spectrum measurement, phenolic OH
Absorption of 3200-3600 cm ^-1 disappears and absorption of epoxide 124
It was confirmed to have an absorption of 0, 910 cm ^-1 .

Synthetic Example 3 In this Synthetic Example, the epoxy resin obtained in Synthetic Example 2, the diglycidyl ether of tetrabromobisphenol A, and tetrabromobisphenol A were added to give
The present invention relates to a method for obtaining a terminal epoxy resin having a bromo content of 20%. Epoxy resin 62.0 obtained in Synthesis Example 2
g, diglycidyl ether of tetrabromobisphenol A (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-
400T, epoxy equivalent 403g / eq) 25.3g, tetrabromobisphenol A 12.7g were charged into a 300 ml four-neck round bottom flask equipped with a thermometer, a cooling tube and a stirrer, and 110 ° C.
It was melted by heating. Then triphenylphosphine 40
A solution prepared by dissolving mg (relative to resin 4 × 10 ⁻⁴ wt%) in 2.2 g of methyl ethyl ketone was added, and the mixture was kept at 110 ° C. for 4 hours to carry out an addition reaction of an epoxy group and a phenolic hydroxyl group. After the reaction, the inside of the system was cooled to 90 ° C. and 22.8 g of methyl ethyl ketone was added dropwise to obtain 123.9 g of a resin solution having a resin solid content of 80.62 wt%. The epoxy equivalent of the obtained resin adduct was 399.0 g / eq.
Met.

Synthetic Example 4 In this Synthetic Example, the epoxy resin obtained in Synthetic Example 2, the diglycidyl ether of tetrabromobisphenol A, and tetrabromobisphenol A were added to give
The present invention relates to a method for obtaining a terminal epoxy resin having a bromo content of 27%. Epoxy resin 132 obtained in Synthesis Example 2.
7 g, diglycidyl ether of tetrabromobisphenol A (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-
400T, epoxy equivalent 403 g / eq) 119.6 g and tetrabromobisphenol A 27.7 g were charged into a 500 ml four-neck round bottom flask equipped with a thermometer, a condenser and a stirrer, and 110 ° C.
It was melted by heating. Then triphenylphosphine 1
12 mg (vs. resin 4 × 10 ^-4 wt%) of methyl ethyl ketone 1.0 g
The solution dissolved in was added and kept at 110 ° C. for 4 hours to carry out the addition reaction of the epoxy group and the phenolic hydroxyl group. After the reaction, the inside of the system was cooled to 90 ° C. and 73.5 g of methyl ethyl ketone was added dropwise to obtain 349.2 g of a resin solution having a resin solid content of 79.80 wt%. The epoxy equivalent of the obtained resin adduct is 388.0 g / eq.
Met.

Synthesis Example 5 This synthesis example relates to a production example of a novolac resin which is a raw material of the epoxy resin (A) which is a constituent component of the resin composition of the present invention. 32-t-butyl-5-methylphenol 328.0 g (2.0 mol), p-toluenesulfonic acid 5.70 g (0.
(03 mol) and 428.0 g of toluene are charged into a 2 liter four-neck round bottom flask equipped with a thermometer, a stirrer, and a condenser with a separation tube, and the temperature is raised to 80 ° C. n-butyraldehyde 10
0.8 g (1.40 mol) was added dropwise using a dropping tube over 2 hours, the temperature was raised, and azeotropic dehydration was performed for 1 hour to remove water generated by the reaction from the system. Then, the temperature was kept at 120 ° C for 2 hours. After the reaction, it was diluted with 571.0 g of toluene and neutralized with 12 g of 10% NaOH aqueous solution. The organic layer after liquid separation was washed twice with 200 g of ion-exchanged water. The washed organic layer was concentrated under reduced pressure (170 ° C./5 mmHg / 0.5 hours) to obtain 259.0 g of a resinous material. OH of the obtained resinous material
The equivalent weight was 192.3 g / eq.

Synthesis Example 6 This synthesis example relates to a production example in which an epoxy resin is obtained by reacting the novolak resin of Synthesis Example 5 with epichlorohydrin. Synthetic example 5 novolak resin 115.4 g (0.6
OHmol), 388.5g (4.2mol) of epichlorohydrin, and 194.3g of dimethylsulfoxide were placed in a 2 liter 4-neck flat bottom flask equipped with a thermometer, a stirrer, and a condenser with a separating tube, and at 54 ° C and 48 torr. 49.38 g (0.6 mol) of 48.6% caustic soda solution was added dropwise over 4 hours. During this time, while keeping the temperature at 55 ° C to 60 ° C, the azeotropic epichlorohydrin and water were cooled and liquefied, and the reaction was performed while returning the organic layer into the reaction system. After the reaction was completed, unreacted epichlorohydrin was removed by concentration under reduced pressure, the epoxidized product containing a byproduct salt and dimethylsulfoxide was dissolved in methyl isobutyl ketone, and the byproduct salt and dimethylsulfoxide were removed by washing with warm water. By removing the solvent under reduced pressure, 138.7 g of an epoxy resin was obtained. The epoxy equivalent of the epoxy resin thus obtained was 305.7 g / eq. Infrared absorption spectrum results Phenolic OH absorption 3200-
3600cm ^-1 disappeared, epoxide absorption 1240, 910cm- ^-1
It was confirmed to have absorption of. The average number of repeating units (n in the general formula (1)) was 0.26.

Synthetic Example 7 In this Synthetic Example, the epoxy resin obtained in Synthetic Example 6 was added to the diglycidyl ether of tetrabromobisphenol A and tetrabromobisphenol A to give an addition reaction.
The present invention relates to a method for obtaining a terminal epoxy resin having a bromo content of 27%. Epoxy resin 42.7 obtained in Synthesis Example 6
g, diglycidyl ether of tetrabromobisphenol A (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-
400 T, epoxy equivalent 403 g / eq) 38.4 g, and tetrabromobisphenol A 8.9 g were charged into a 300 ml four-neck round bottom flask equipped with a thermometer, a condenser and a stirrer, and heated and melted at 110 ° C. Triphenylphosphine 18mg (against resin
A solution prepared by dissolving 4 × 10 ⁻⁴ wt%) in 1.8 g of methyl ethyl ketone was added, and the mixture was kept at 110 ° C. for 4 hours to carry out an addition reaction between an epoxy group and a phenolic hydroxyl group. After the reaction, the inside of the system was cooled to 90 ° C., and 20.7 g of methyl ethyl ketone was added dropwise to obtain 112.0 g of a resin solution having a resin solid content of 80.35 wt%. The epoxy equivalent of the obtained resin adduct was 355.6 g / eq.

Synthesis Example 8 This synthesis example relates to a production example of a novolak resin which is a raw material of the epoxy resin (A) which is a constituent component of the resin composition of the present invention. Cyclohexylphenol (o-, p-
(Isomer mixture) 317.4 g (1.8 mol), p-toluenesulfonic acid 20.6 g (0.108 mol), and toluene 300.0 g were placed in a 500 ml four-neck round bottom flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was 80 ° C. The temperature rises to. 37% formalin 109.5g (1.35mol)
Was added dropwise over 3 hours using a dropping tube to raise the temperature and kept at 90 ° C. for 9 hours. After the reaction, leave still and separate the aqueous layer, 500 g
It was washed 6 times with ion-exchanged water. The washed organic layer was concentrated under reduced pressure (170 ° C./5 mmHg / 0.5 hours) to obtain 305.4 g of a resinous material. The OH equivalent of the obtained resinous material was 185.9 g / eq.

Synthesis Example 9 This synthesis example relates to a production example in which an epoxy resin is obtained by reacting the novolak resin of Synthesis Example 8 with epichlorohydrin. 130.1 g (0.7%) of the novolak resin of Synthesis Example 8
OHmol), 453.3 g (4.9 mol) of epichlorohydrin, and 194.3 g of dimethyl sulfoxide were placed in a 2-liter 4-neck flat-bottomed flask equipped with a thermometer, a stirrer, and a condenser with a separation tube, under the conditions of 48 ° C and 41 torr. Then, 57.61 g (0.7 mol) of 48.6% aqueous sodium hydroxide solution is added dropwise over 8 hours. During this time,
While maintaining the temperature at 48 ° C., the azeotropic epichlorohydrin and water were cooled and liquefied, and the reaction was performed while returning the organic layer to the reaction system. After the reaction was completed, unreacted epichlorohydrin was removed by concentration under reduced pressure, the epoxidized product containing a byproduct salt and dimethylsulfoxide was dissolved in methyl isobutyl ketone, and the byproduct salt and dimethylsulfoxide were removed by washing with warm water. Epoxy resin by removing the solvent under reduced pressure
156.1 g was obtained. The epoxy equivalent of the epoxy resin thus obtained was 284.0 g / eq. Absorption 3200-3600Cm ^-1 results phenolic OH infrared absorption spectrum measurement disappeared and it was confirmed that the absorption of epoxide absorption 1240, 910 cm ^-1.

Synthetic Example 10 In this Synthetic Example, the addition reaction of the epoxy resin obtained in Synthetic Example 9, the diglycidyl ether of tetrabromobisphenol A, and tetrabromobisphenol A was conducted.
The present invention relates to a method for obtaining a terminal epoxy resin having a bromo content of 27%. Epoxy resin 94.8 obtained in Synthesis Example 9
g, diglycidyl ether of tetrabromobisphenol A (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-
400T, epoxy equivalent 403g / eq) 85.4g, and tetrabromobisphenol A 19.8g were charged into a 300 ml four-neck round bottom flask equipped with a thermometer, a cooling tube and a stirrer, and 110 ° C.
It was melted by heating. A solution prepared by dissolving 80 mg of triphenylphosphine (compared to resin 4 × 10 ⁻⁴ wt%) in 1.5 g of methyl ethyl ketone was added, and the mixture was kept at 110 ° C. for 4 hours to carry out an addition reaction between an epoxy group and a phenolic hydroxyl group. After the reaction, the system was cooled to 90 ° C. and 50.0 g of methyl ethyl ketone was added dropwise to obtain 247.3 g of a resin solution having a resin solid content of 80.17 wt%. The epoxy equivalent of the obtained resin adduct was 425.1 g / eq.

Synthesis Example 11 This synthesis example relates to a production example of a polycyanate compound which is a constituent component of the resin composition of the present invention. Bisphenol A 200.0 g (0.877 mol), chlorcyan 129.1 g (2.1
(05 mol) and 467.0 g of acetone were placed in a 2 liter four-necked flat-bottom separable flask equipped with a thermometer, a stirrer and a reflux condenser, and dissolved at -3 ° C. Triethylamine 186.4g
(1.846 mol) was added dropwise using a dropping tube over 2 hours. After the dropping, the temperature was raised to 8 ° C. and kept for 1 hour. The reaction solution was filtered to remove salts, then precipitated in water, filtered and dried under reduced pressure to obtain 176.0 g of the desired compound as crystals. The polycyanate compound thus obtained, the absorption of phenolic OH 3200-3600 cm ^-1 disappeared as a result of infrared absorption spectrum measurement,
It was confirmed that the nitrile had an absorption of 2250 cm ^-1 .

Synthesis Example 12 This synthesis example relates to a production example of a polycyanate compound which is a constituent component of the resin composition of the present invention. 1,1
-Bis (5-t-butyl-2-methyl-4-hydroxyphenyl) butane (Sumitomo Chemical Co., Ltd., trade name Sumilizer BBM-S) 200.0 g (1.05 OHmol), acetone 800.0
Charge g into a 2 liter 4-neck flat bottom separable flask equipped with a thermometer, stirrer and reflux condenser, dissolve and
Cooled to ° C. Chlorcyan 77.3 g (1.26 mol) was added, and then triethylamine 111.3 g (1.10 mol) was added at a reaction temperature of 0.
The solution was added dropwise over 1 hour, taking care not to exceed ℃. After the dropping, the temperature was raised to 2 to 5 ° C and the temperature was maintained for 1 hour. After the reaction was completed, the mixture was diluted with 500.0 g of chloroform, filtered to remove salts, washed with water, and the solvent was distilled off under reduced pressure to give a resinous material 194.
8 g were obtained. The polycyanate compound thus obtained showed a phenolic OH as a result of infrared absorption spectrum measurement.
Absorption 3200-3600Cm ^-1 disappeared, to have absorption in the absorption of a nitrile of cyanate 2270 cm ^-1 was confirmed.

Examples 1 to 8 Epoxy resins obtained in Synthesis Examples 4, 7 and 10, diglycidyl ether of tetrabromobisphenol A (manufactured by Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-400T, epoxy equivalent 403 g) / eq), polycyanate compounds obtained in Synthesis Examples 11 and 12, phenol-added polybutadiene resin (manufactured by Nippon Oil Co., Ltd., trade name PP-700-300), 2-ethyl-4-methylimidazole and zinc naphthenate. Table 1
Were mixed in the ratio shown in Table 1 and dissolved in methyl ethyl ketone to obtain a uniform resin varnish. Glass varnish (trade name)
KS-1600S962LP, manufactured by Kanebo Co., Ltd., was impregnated and treated with a hot air dryer at 150 ° C. for 5 to 10 minutes to obtain a prepreg. Five prepregs and copper foil (TSTO treated 35 μm thick, Furukawa Circuit Foil Co., Ltd.) are overlaid, and 170 ℃ × 50kg / cm ² × 12
It was heat-pressed for 0 minutes to obtain a copper-clad laminate having a thickness of 1 mm. The boiling water absorption and the solder heat resistance of the laminate were measured according to JIS-C-6481. The glass transition temperature (Tg) was obtained from the inflection point of the thermal expansion curve using a thermal analyzer DT-30 manufactured by Shimadzu Corporation. The dielectric constant and the dielectric loss tangent at room temperature were calculated using Yokogawa Hewlett-Packard Co., Ltd.'s 4275A Multi-Frequency LCR meter, and the value of the dielectric constant was calculated from the capacitance of the sample.
Table 1 shows the measurement results.

Examples 9 to 10 Epoxy resin obtained in Synthesis Example 3, polycyanate compound obtained in Synthesis Examples 11 and 12, dicyandiamide, 2
-Ethyl-4-methylimidazole and zinc naphthenate were mixed in the proportions shown in Table 1 and dissolved in a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether to form a uniform resin varnish. Example 1 using the varnish
A 1 mm thick copper clad laminate was obtained in the same manner as in. The physical properties of the laminated plate were also measured in the same manner as in Example 1. Table 2 shows the measurement results
Shown in

Comparative Example 1 Brominated epoxy resin (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-500, epoxy equivalent)
472g / eq) and cresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESCN-22)
0, epoxy equivalent 215 g / eq), dicyandiamide and 2-ethyl-4-methylimidazole were mixed in the ratio shown in Table 1 and dissolved in a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether to form a uniform resin varnish. Glass varnish (trade name KS-160)
The prepreg was obtained by impregnating 0S962LP with Kanebo Co., Ltd. and treating with a hot air dryer at 150 ° C. for 5 to 10 minutes. Prepreg 5
The sheet and a copper foil (TSTO-treated 35 μm thick, manufactured by Furukawa Circuit Foil Co., Ltd.) were overlaid and subjected to hot press molding at 160 ° C. × 50 kg / cm ² × 90 minutes to obtain a 1 mm thick copper clad laminate. The physical properties of the laminate were measured in the same manner as in Example 1 and the results are shown in Table 2.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

EFFECTS OF THE INVENTION The cured resin of the thermosetting resin composition of the present invention has excellent dielectric properties, and the copper-clad laminate molded using the same has the excellent physical properties described above, and thus has a multilayer print for high-speed arithmetic processing. Suitable for wiring boards.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 73/00 NTB H05K 1/03 610 L 7511-4E

Claims (4)

[Claims] (1) (A) General formula (1): (In the formula, n represents an average number of repetitions and takes a value of 0 or more and 10 or less. R ₁ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. P independently represents at least one carbon atom. An alkyl group having 4 to 9 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, the other is an alkyl group having 1 to 9 carbon atoms, and i is independently an integer value of 1 or more and 3 or less. . If i is 2 or more, P
May be the same or different in the same ring. ) And an epoxy resin (B) represented by the general formula (2) (In the formula, R ₂ represents a hydrogen atom or a methyl group, and two R ₂ may be the same or different.
X and X ′ are halogen atoms, and they may be the same or different from each other. k and l are 1 independently
It is an integer not less than 4 and not more than 4. ) And a compound obtained by previously reacting with a halogen-containing bisphenol compound represented by
(2) Thermosetting resin composition in which a polycyanate compound having two or more cyanate groups in the molecule and (3) an epoxy curing agent are essential components, and the content of the polycyanate compound is 5 to 50% by weight. Stuff. 2. The polycyanate compound of (2) among the components of the thermosetting resin composition according to claim 1, is represented by the general formula (3): (In the formula, R ₃ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and two R ₃ may be the same or different. Q and Q ′ are alkyl groups having 1 to 9 carbon atoms,
It represents a cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, which may be the same or different. j and m are independently 0 or more and 4
It is the following integer. The thermosetting resin composition which is a compound represented by these. 3. A thermosetting resin composition, wherein the epoxy curing agent (3) is a polybutadiene compound modified with phenols, among the components of the thermosetting resin composition according to claim 1 or 2. 4. A thermosetting resin copper obtained by heat-molding a prepreg obtained by dissolving the thermosetting resin composition according to claim 1, 2 or 3 in an organic solvent and impregnating the base material with a copper foil. Upholstered laminate.