JPH1071674A - Copper clad laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copper clad laminated sheet excellent in low dielectric constant properties and low dielectric loss tangent properties by heating and molding a prepreg obtained by using a thermosetting resin compsn. containing an aryl ester compd., an epoxy resin and a curing catalyst as essential components and copper foil. SOLUTION: Polyhydric phenol of an aryl ester compd. used in a thermosetting resin compsn. of a copper clad laminated sheet is synthesized by the condensing reaction of resorcinol represented by formula I and a carbonyl compd. represented by formula II in the presence of an acid catalyst. In the formula I, P is respectively independently a hydrogen atom, a halogen atom, a 1-10C alkyl group, a 5-10C cycloalkyl group, a 6-20C aryl group or a 7-20 aralkyl group and i is an integer of 0-2. In the formula II, X and X' are a hydrogen atom, a 1-10C alkyl group, 5-10C cycloalkyl group, a 6-20C aryl group or a 7-20C aralkyl group and may form a ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a copper-clad laminate using a thermosetting resin composition having excellent low dielectric loss tangent and low dielectric constant. The copper-clad laminate of the present invention is particularly useful as a printed wiring board requiring low dielectric properties.

[0002]

2. Description of the Related Art Among epoxy resins used for electric and electronic applications, a combination of a bisphenol type epoxy resin and dicyandiamide is mainly used as a material for a printed wiring board. In recent years, as the printed wiring board has become thinner and more multilayered, the resin has a low dielectric constant for the purpose of improving the signal speed and impedance matching of the circuit. Are required to have a low dielectric loss tangent. In contrast, a method has been devised in which a conventional epoxy resin is combined with a thermoplastic resin having a low dielectric constant and a low dielectric loss tangent. For example, a method of modifying with a reactive polybutadiene resin, a method of dispersing a powder of polytetrafluoroethylene resin, and the like. However, in these conventional techniques, since the basic epoxy resin has a high dielectric constant, the ratio of the thermoplastic resin to be combined increases to achieve a desired dielectric constant. Properties, dimensional stability, chemical resistance, etc. are impaired. And the copper-clad laminate using such a combination of resins was inferior in these properties.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to improve the heat resistance, low dielectric constant, low dielectric loss tangent, etc. without impairing the characteristics of a copper-clad laminate obtained using a conventional epoxy resin. It is to provide an excellent copper-clad laminate.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on the functional group structure and skeletal structure of a compound capable of undergoing thermosetting reaction with an epoxy resin. It has been found that a copper-clad laminate using an epoxy resin composition in combination with the above satisfies the above objects, and has accomplished the present invention. That is, the present invention is as follows. (1) (A) The following general formula (1)

[0005]

Embedded image (Wherein, P is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms) Represents an aralkyl group of 20. i represents an integer value of 0 or more and 2 or less), and a resorcinol represented by the following general formula (2)

[0006]

Embedded image (In the formula, X and X ′ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. And X and X ′ may form a ring. At least one of the OH groups of the polyhydric phenol which is a condensation product with the carbonyl compound represented by the formula An aryl ester compound esterified with an organic acid having 1 to 20 carbon atoms or a derivative thereof, which contains an organic polyacid having 1 to 20 or a derivative thereof, (B) an epoxy resin, and (C) a curing catalyst A copper-clad laminate obtained by heating and molding a prepreg and a copper foil obtained using a thermosetting resin composition containing, as essential components. (2) The polyhydric phenol which is a raw material of the ester compound as the component (A) is represented by the following general formula (3)

[0007]

Embedded image (In the formula, n is the average number of repetitions and is 1 or more and 20 or less. P is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, i represents an integer of 0 to 2. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ Is
Each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or represents an aralkyl group having a carbon number of 7 to 20, R ₁ And R ₂ , and R ₄ and R ₅ may each independently form a ring. A copper-clad laminate obtained by heating and molding a prepreg obtained by using the thermosetting resin composition according to (1), which is a compound represented by (1), and a copper foil. (3) carbon number 1 to be used for synthesizing component (A)
The organic acid having 20 or a derivative thereof has 1 to 1 carbon atoms.
The copper-clad laminate according to (1) or (2), comprising 10 to 50% of an organic polyacid having 20 or a derivative thereof. (4) The thermosetting resin composition according to (1) or (2), wherein the thermosetting resin composition contains (D) a flame retardant as an essential component in addition to the components (A), (B), and (C). Copper clad laminate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyhydric phenol which is an intermediate for producing an ester compound used in the present invention comprises a resorcinol represented by the above general formula (1) and a carbonyl represented by the above general formula (2). The compound is synthesized by a known method such as a condensation reaction in the presence of an acid catalyst. As the resorcinols, those having no substituent at the 4- and 6-positions are used [general formula (1)]. Examples thereof include resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2-propylresorcinol, 2-n
-Butyl resorcinol, 5-isobutyl resorcinol, 5-t-butyl resorcinol, 5-octyl resorcinol, 5-nonyl resorcinol, 2,5-dimethyl resorcinol, 2,5-diethyl resorcinol, 2,5-diisopropyl resorcinol, 2-methyl Alkyl resorcinols such as -5-butyl resorcinol, 2-methyl-5-nonyl resorcinol, etc., or 2-cyclopentyl resorcinol,
Cycloalkyl resorcinols such as cyclohexyl resorcinol and 2-cycloheptyl cresol, aryl resorcinols such as 5-phenyl resorcinol and 5-naphthyl resorcinol, and aralkyl resorcinols such as 5-benzyl resorcinol and 5-phenethyl resorcinol , 2-chlororesorcinol, 5-chlororesorcinol, 2,
Halogenated resorcinols such as 5-dichlororesorcinol, 2-bromoresorcinol, 5-bromoresorcinol, 2,5-dibromoresorcinol, 2-iodoresorcinol, 5-iodoresorcinol, and 2,5-diiodoresorcinol;

Examples of the carbonyl compound (general formula (2)) include aldehydes represented by formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, phenylacetaldehyde, cyclohexylacetaldehyde, acetone, methyl ethyl ketone, diethyl ketone, Ketones such as methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, cycloheptanone, benzyl phenyl ketone, benzyl methyl ketone, methyl phenethyl ketone, acetophenone, acetonaphthenone, indan-1-one and the like.

Examples of the acid catalyst used in the condensation reaction between resorcinols and carbonyl compounds include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid, acidic clay, activated alumina and the like. , Zeolite and other solid acids, and acidic ion exchange resins. The amount of these acid catalysts is preferably 0.01 to 50% by weight, more preferably 0.5 to 20% by weight, based on the sum of the weights of the resorcinols and the carbonyl compound charged as raw materials. In the condensation reaction, a known non-reactive organic solvent may be used, and toluene,
Xylene, dioxane, tetrahydrofuran, N, N-
Examples include, but are not limited to, dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, and the like. The molar ratio of resorcinols to carbonyl compounds at the time of the condensation reaction is from 0.1 to 2.0, preferably from 0.3 to 1.5. Exceeding this range causes a problem that excessive resorcinols remain or OH residues of the product decrease. The reaction temperature is
It is preferably carried out at 0 to 200 ° C, more preferably at 20 ° C.
１６０160 ° C. Above this range, lower temperatures result in lower conversions and higher temperatures produce large amounts of by-products. The reaction time is preferably 1 to 100 hours, more preferably 2 to 80 hours. Beyond this range,
When the time is short, the reaction is incomplete, and the yield does not change even if the reaction is performed for a longer time, which is not economical. At the time of the condensation reaction, water generated by the reaction may or may not be removed from the system. In the case of removal, the reaction may be carried out using an apparatus such as a Dean-Stark tube capable of performing a reaction while removing water in the system using a solvent capable of azeotropic dehydration such as toluene and xylene. Further, the reaction may be performed under reduced pressure to promote dehydration.

More preferably, the ester compound used in the present invention is a raw material polyhydric phenol,
It is a compound represented by the general formula (3). In the above formula, P is derived from the resorcinols of the general formula (1), and the examples of the resorcinols are referred to above. In R _{1 to} R ₅ , the number of carbon atoms is 1
The alkyl group of 10 to 10, the cycloalkyl group of 5 to 10 carbon atoms, the aryl group of 6 to 20 carbon atoms, and the aralkyl group of 7 to 20 carbon atoms are derived from the carbonyl compound of the general formula (2), As examples thereof, the examples of the above-mentioned carbonyl compounds can be referred to. In the general formula (3), n is
It represents the average repetition number and can take a value of 1 or more and 20 or less, but from 1 to 10 is preferable from the viewpoint of operability.

The polyhydric phenol which is a condensation product is esterified in the presence of a base by reacting with an organic acid having 1 to 20 carbon atoms or a derivative thereof. Among the organic acids and derivatives thereof, the organic polyacids and derivatives thereof essential for the synthesis of the ester compound of the present invention are organic compounds having two or more carboxyl groups and acid anhydrides or acid halides thereof. Aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, citraconic acid and their acid halides and anhydrides, phthalic acid, isophthalic acid, terephthalic acid, Aromatic polycarboxylic acids such as naphthalenedicarboxylic acid, benzenetricarboxylic acid and the like and their acid halides and anhydrides, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid and the like and their acids Halides and acid anhydrides Although it is not intended to be limited thereto. Examples of organic acids and derivatives thereof other than the above include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, phenylacetic acid, and bromoacetic acid, and their acid halogens. And acid anhydrides, benzoic acid, methylbenzoic acid, naphthoic acid, aromatic monocarboxylic acids such as biphenylcarboxylic acid and their acid halides and acid anhydrides, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid And the like, but not limited thereto. Among the organic acids or derivatives thereof having 1 to 20 carbon atoms used for the esterification, the organic polyacids or derivatives thereof having 1 to 20 carbon atoms are preferably 10 to 50%, and if less than this, the epoxy resin composition When the heat resistance of the cured product of the compound (1) is lowered, if it is higher than this, the molecular weight becomes high at the time of synthesis of the ester compound, and further the gelation occurs. Examples of the basic compound used in the esterification reaction include inorganic base compounds such as sodium hydroxide and potassium hydroxide, and organic base compounds such as pyridine, triethylamine, triphenylphosphine, and imidazole compounds. In the esterification reaction, a known organic solvent may be used, and toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dioxane, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. Although exemplified, toluene, xylene and methyl isobutyl ketone are preferred.

The molar equivalent ratio of all the organic acids or derivatives thereof used in the esterification reaction to the OH group of the polyhydric phenol is from 0.3 to 2.0, more preferably from 0.1 to 2.0.
5 to 1.5. If it exceeds this range, there is a problem that an excessive amount of the organic acid remains or the acylation rate of the product decreases. The reaction is carried out at a temperature of from 20 to 200 ° C., preferably from 40 to 150 ° C. When the temperature exceeds this range, the addition rate decreases when the temperature is low, and a large amount of by-products are generated when the temperature is high. The reaction time is 2 to 50 hours,
More preferably, it is 4 to 30 hours. If it exceeds this range, the reaction is incomplete if the time is short, and the yield does not change even if the reaction is carried out for a longer time, which is not economical.
When the organic acid itself is used as a raw material in the ester reaction, water generated by the reaction may or may not be removed from the system. In the case of removal, the reaction may be carried out using a solvent such as toluene, xylene, methyl isobutyl ketone or the like which can be reacted while removing water in the system using an azeotropic dehydration solvent such as toluene, xylene and methyl isobutyl ketone. Further, the reaction may be performed under reduced pressure to promote dehydration.

Examples of the epoxy resin used in the present invention include known compounds containing two or more epoxy groups in a molecule, and the chemical structure is not particularly limited. For example, bifunctional epoxy such as diglycidyl ether of bisphenol A, diglycidyl ether of tetrabromobisphenol A, or glycidyl ether of tris (4-hydroxyphenyl) methane, 1,1,1-tris (4 Trifunctional epoxy such as glycidyl ether of -hydroxyphenyl) ethane,
Alternatively, glycidyl ether of phenol novolak, glycidyl ether of cresol novolak, glycidyl ether of novolak obtained by dehydration condensation of phenols and hydroxyaryl aldehydes,
Polyfunctional epoxy such as glycidyl ether of poly (4-hydroxystyrene), glycidyl ether of phenol-modified polybutadiene, glycidyl ether of phenol-dicyclopentadiene adduct, glycidyl ether of bisphenol A novolak, epoxy resin and bisphenol A, resorcinol A product obtained by previously reacting a phenol compound such as tetrabromobisphenol A or tetrachlorobisphenol A,
A mixture of two or more epoxy resins, and the like,
In order to provide the low dielectric property which is the object of the present invention, an epoxy resin having at least one alkyl group having 4 or more carbon atoms in the aromatic nucleus as a substituent is more preferable. Glycidyl ether of novolak of t-butyl-5-methylphenol, glycidyl ether of cyclohexylphenol novolak, glycidyl ether of octylphenol novolak, 1,1-
Diglycidyl ether of (4-hydroxy-5-t-butyl-2-methylphenyl) butane, limonenebis (2
-Sec-butylphenol).

The quantitative ratio of the epoxy resin to the ester compound in the present invention is such that the ratio of the number of moles of the epoxy group in the epoxy resin to the number of moles of the ester group in the ester compound is 1: 0.3 to 1: 1. It is preferable to mix them so as to be 0.5, more preferably in the range of 1: 0.5 to 1: 1.2. If it is out of this range, poor curing occurs, and a good cured product cannot be obtained. As the flame retardant used in the present invention, a known flame retardant can be arbitrarily used regardless of an organic compound or an inorganic compound. Among them, glycidyl ether of tetrabromobisphenol A and glycidyl ether of bromo-containing phenol novolak are particularly preferred from the viewpoint of availability and the like, but are not limited thereto. These flame retardants can be blended in the resin composition in an arbitrary ratio, but when used as a resin composition for a printed wiring board, UL which is a guide to flame retardancy is usually used.
Add to the extent that standard V-0 can be achieved. If added more than necessary, properties such as Tg and dielectric constant will be reduced.

The curing catalyst used in the present invention is an ordinary compound which accelerates the curing reaction between the epoxy resin and the curing agent. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and 4-methylimidazole;
Tertiary amines such as triethylamine, benzyldimethylamine, 1,4-diazabicyclo [2.2.2] undecene; quaternary ammonium salts such as tetra-n-butylammonium bromide and tetra-n-amylammonium bromide; triphenyl And phosphorus-based compounds such as phosphine. Further, it is desirable to add such a quantitative ratio so as to be 0.05 to 3% by weight in the whole resin. It is also possible to use a thermosetting resin other than the epoxy resin, a thermoplastic resin having a functional group, or the like in combination without impairing the effects of the present invention. Specific examples include a cyanate resin, a maleimide resin, glycidyl-modified polybutadiene, and maleic anhydride-modified polyethylene. In the present invention, known additives such as a release agent, a surface treatment agent, and a filler may be added to the composition depending on the use. Examples of the release agent include waxes and zinc stearate, and examples of the surface treatment agent include a silane coupling agent. Silica as a filler,
Alumina, talc, clay and the like can be mentioned.

The production of the copper-clad laminate of the present invention can be performed by any method. As a general manufacturing method, a resin varnish, which is a solution obtained by dissolving a thermosetting resin composition in an organic solvent, is impregnated into a base material, and then heat-treated to form a prepreg. However, the method is not limited to this. As the organic solvent used, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, toluene, xylene, 1,4-dioxane, tetrahydrofuran, N, N-dimethylformamide and the like, or a mixture of two or more thereof. Examples of the substrate to be impregnated with the resin varnish include woven fabric, nonwoven fabric, mat, paper made of inorganic or organic fiber such as glass fiber, alumina fiber, polyester fiber and polyamide fiber, or a combination thereof. The heat treatment conditions for the prepreg are appropriately selected according to the type and amount of the solvent, the added catalyst, and other various additives to be used.
The reaction is performed at a temperature of 00 ° C to 200 ° C for 3 minutes to 30 minutes. As a method of laminating the prepreg and the copper foil and forming by heating, a temperature of 150 ° C. to 300 ° C. and 10 kg / cm ² to
An example is a method of hot press molding at a molding pressure of 100 kg / cm ² for a period of 20 minutes to 300 minutes. The copper-clad laminate of the present invention is used for a printed wiring board requiring low dielectric constant, low dielectric loss tangent, and low water absorption. Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, the epoxy equivalent refers to an epoxy group 1
The OH equivalent is defined by the molecular weight of the epoxy resin per unit, and the OH equivalent is defined by the molecular weight of the polyphenol compound per OH group.

[0018]

【Example】

Synthesis Example 1 This synthesis example relates to a method for producing a glycidyl ether of novolac of 2-t-butyl-5-methylphenol, which is a raw material of an epoxy resin used for the thermosetting resin composition of the copper-clad laminate of the present invention. It is. 2-t-butyl-5-
Methylphenol 2231.0 g (13.58 OHmol eq.), P-toluenesulfonic acid 12.9 g (0.068 mol), ion-exchanged water 22
3.2g was equipped with a thermometer, stirrer, cooling pipe and dropping pipe.
Charge into a 4-liter round bottom flask and heat to 100 ° C. After 218.4 g (2.715 mol) of 37% formalin was added dropwise over 2 hours, the reaction was carried out by keeping the temperature at 100 ° C. for 2 hours.
After that, it was cooled to 80 ° C and 27.7 g (0.069m
ol). The separated organic layer was washed twice with 700 g of ion-exchanged water. The organic layer after washing is concentrated under reduced pressure (180 ° C / 10
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. 246.4 g (1.4 OH mol eq.) Of the reaction product obtained as described above, 906.5 g (9.8 mol) of epichlorohydrin, 45 dimethyl sulfoxide
3.3 g and 14.0 g of ion-exchanged water were charged into a 2 liter four-necked round bottom flask equipped with a thermometer, a stirrer, and a cooling tube equipped with a separation tube, and 108.31 g of a 48.6% aqueous sodium hydroxide solution (1.316 mol) is added dropwise over 5 hours. During this time, while maintaining the temperature at 49 ° C., azeotropic epichlorohydrin and water were cooled and liquefied, and the reaction was performed while returning the organic layer into the reaction system. After completion of the reaction, unreacted epichlorohydrin was removed by concentration under reduced pressure, an epoxidized product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone, and the by-product salt and dimethyl sulfoxide were removed by washing with warm water. By removing the solvent under reduced pressure, 304.9 g of an epoxy resin was obtained. The epoxy equivalent of the epoxy resin thus obtained was 256 g / eq. As a result of infrared absorption spectrum measurement, absorption of phenolic OH 3200-3
600 cm ^-1 disappeared and it was confirmed that the absorption of epoxide absorption 1240,910cm ^-1.

Synthesis Example 2 In this synthesis example, an addition reaction of the epoxy resin obtained in Synthesis Example 1 with the diglycidyl ether of tetrabromobisphenol A and tetrabromobisphenol A was carried out.
The present invention relates to a method for obtaining a terminal epoxy resin. 83.8 g of the epoxy resin obtained in Synthesis Example 1, diglycidyl ether of tetrabromobisphenol A (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiepoxy ESB-400, epoxy equivalent: 4)
03g / eq) 75.5 g, tetrabromobisphenol A 17.5
g and 15.9 g of methyl ethyl ketone were charged into a 300 ml four-necked round-bottomed flask equipped with a thermometer, a condenser and a stirrer, and were heated and melted at 110 ° C. Thereafter, 0.71 g of a 10% solution of triphenylphosphine in methyl ethyl ketone (weight ratio of triphenylphosphine to resin: 4 × 10 ⁻⁴ ) 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 63.5 g of propylene glycol monomethyl ether was added dropwise to obtain 250 g of a resin solution having a resin solid content of 70 wt%. The epoxy equivalent of the obtained resin adduct was 390.0 g / eq. In terms of solid content.

Synthesis Example 3 In this synthesis example, a polyhydric phenol, 2,4,4-trimethyl-2- (2), which is a raw material of an arylester compound used for the thermosetting resin composition of the copper-clad laminate of the present invention, is used. , 4-Dihydroxyphenyl) -7-hydroxychroman (CAS
No. 26505-28-2). Resorcinol 1000.0 g (9.1 mol), p-toluenesulfonic acid 6.
9 g (0.036 mol), methanol 330.0 g, acetone 176.0 g
(3.0 mol) was charged into a 5-liter 4-neck round bottom flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel, and the temperature was raised to 65 ° C. After maintaining at 65 ° C. for 9 hours, 750 g of ion-exchanged water was charged, and the mixture was maintained at 40 ° C. for 3 hours, and the precipitated crystals were filtered and washed. The obtained crude crystals were dissolved in methanol and then recrystallized by adding dropwise ion-exchanged water. The yield after filtration and drying under reduced pressure was 265 g. 1H-NMR and IR confirmed that it was the target compound.

Synthesis Example 4 This synthesis example relates to a method for producing an aryl ester compound used in the thermosetting resin composition of the copper-clad laminate of the present invention. The 2L four-necked flask equipped with a cooling tube, a thermometer, a stirrer, and a dropping device was charged with 2,2 obtained in Synthesis Example 3.
70 g (0.7 moleq.) Of 4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman,
Charge 77.8 g (0.77 moleq.) Of triethylamine and 300.8 g of MIBK (methyl isobutyl ketone) and raise the temperature to 70 ° C. 21.3 g (0.21 moleq.) Of terephthalic dichloride was added to MI
After the slurry solution dissolved in 168.0 g of BK is dropped in 30 minutes, 57.1 g (0.56 moleq.) Of acetic anhydride is dropped in 1 hour. After raising the temperature to 90 ° C. and keeping it for 5 hours, it was washed with water to remove salts, and the solvent was removed under reduced pressure to obtain 96.9 g of a resinous solid. Infrared absorption spectrum: 2970, 1760 (carbonyl stretch of acetate), 1740 (carbonyl stretch of terephthalate), 1605, 1580, 1490, 1410, 1365, 1240, 120
0, 1145, 1120, 1100, 1070, 1055, 1010, 900, 720 cm
No absorption by -1OH stretching vibration was observed.

Synthesis Example 5 This example relates to a method for producing an ester compound used in the thermosetting resin composition of the copper-clad laminate of the present invention.
The 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7- obtained in Synthesis Example 3 was placed in a 2 L four-necked flask equipped with a cooling tube, a thermometer, a stirring device, and a dropping device.
Hydroxychroman 70 g (0.7 moleq.), Triethylamine 77.8 g (0.77 moleq.), MIBK 189.0 g were charged, and 70
Heat to ° C. Isophthalic dichloride 21.3 g (0.21 m
oleq.) in 190.0 g of MIBK is added dropwise over 30 minutes, and then 57.1 g (0.56 moleq.) of acetic anhydride is added dropwise over 1 hour. After elevating the temperature to 90 ° C. and keeping the temperature for 5 hours, it was washed with water to remove salts, and the solvent was removed under reduced pressure to obtain 73.2 g of a resinous solid. Infrared absorption spectrum: 2970, 1765 (carbonyl stretching of acetate ester), 1740 (shoulder) (carbonyl stretching of isophthalic ester), 1610, 1585, 1495, 1420, 1375,
1300, 1210, 1145, 1125, 1055, 1015, 900, 755 cm ^-1
No absorption by OH stretching vibration was observed.

Examples 1 to 4 This example relates to a production example of a copper-clad laminate using the thermosetting resin composition for a copper-clad laminate of the present invention.
Thermosetting resin composition blended in the blending ratio described in Table 1
50 g was dissolved in MEK to obtain a uniform resin varnish having a resin content of 60%. Place the varnish on a glass cloth (trade name KS)
1600S962LP, manufactured by Kanebo Co., Ltd.)
A prepreg was obtained by treating with a hot air dryer at 60 ° C. for 6 minutes.
5 prepregs and copper foil (TSTO treatment, 35 μm thickness,
Furukawa Circuit Wheel Co., Ltd.), 170 ℃
For 2 hours to obtain a copper-clad laminate having a thickness of 1 mm. Table 1 shows the physical properties of the obtained copper-clad laminate.

Comparative Example 1 Thermosetting resin composition blended in the blending ratio shown in Table 1
50 g was dissolved in DMF (dimethylformamide) to obtain a uniform resin varnish having a resin content of 60%. The resin varnish was heated and stirred to perform prepolymerization at 90 ° C. for 2 hours. The varnish is applied to a glass cloth (trade name KS-1600S).
962 LP, manufactured by Kanebo Co., Ltd.) and treated with a hot-air dryer at 150 ° C. for 6 minutes to obtain a prepreg. Five prepregs and a copper foil (TSTO treatment, 35 μm thickness, manufactured by Furukawa Circuit Foil Co., Ltd.) were overlapped and hot pressed at 160 ° C. for 2 hours to obtain a 1 mm-thick copper-clad laminate. Table 1 shows the physical properties of the obtained copper-clad laminate. In Table 1, physical properties were measured by the following methods. -Glass transition temperature (Tg): It was determined from the inflection point of the thermal expansion curve using a thermomechanical analyzer DT-30 manufactured by Shimadzu Corporation. -Dielectric constant and dielectric loss tangent: Measured using an impedance analyzer 4291A manufactured by Hewlett-Packard Japan. Water absorption: The sample was immersed in boiling water for 48 hours, and then calculated from the change in weight. -Copper foil peeling strength was measured according to JIS-C-6481.

[0025]

[Table 1]

The copper-clad laminate of the present invention has excellent heat resistance, low dielectric constant, low dielectric loss tangent, etc., without deteriorating the characteristics of the copper-clad laminate obtained by using the conventional epoxy resin. It is particularly suitable for a multilayer printed wiring board for high-speed arithmetic processing or high-frequency communication.

Claims (4)

[Claims] (A) The following general formula (1): (Wherein, P is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms) Represents an aralkyl group of 20. i represents an integer value of 0 or more and 2 or less), and a resorcinol represented by the following general formula (2): (In the formula, X and X ′ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. And X and X ′ may form a ring. At least one of the OH groups of the polyhydric phenol which is a condensation product with the carbonyl compound represented by the formula An ester compound esterified with an organic acid having 1 to 20 carbon atoms or a derivative thereof, which necessarily contains an organic polyacid having 1 to 20 or a derivative thereof,
A copper-clad laminate obtained by laminating a copper foil and a prepreg obtained by using a thermosetting resin composition containing (B) an epoxy resin and (C) a curing catalyst as essential components, and heat molding. 2. The polyhydric phenol used as a raw material of the ester compound as the component (A) is represented by the following general formula (3). (In the formula, n is the average number of repetitions and is 1 or more and 20 or less. P is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, i represents an integer of 0 to 2. R ₁ , R ₂ , R ₃ , R ₄ , R ₅
Are each independently a hydrogen atom or a group having 1 to 10 carbon atoms.
An alkyl group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, wherein R ₁ , R ₂ and R ₄ and R _4
5 may each independently form a ring. The copper-clad laminate according to claim 1, which is a compound represented by the formula: 3. The organic acid having 1 to 20 carbon atoms or a derivative thereof used for synthesizing the component (A) is an organic acid having 1 to 20 carbon atoms or a derivative thereof having 10 to 10 carbon atoms.
The copper-clad laminate according to claim 1 or 2, which contains 50%. 4. A thermosetting resin composition comprising (A), (B),
The copper-clad laminate according to any one of claims 1 to 3, wherein (D) a flame retardant is an essential component in addition to the component (C).