JPH06246871A - Copper plated epoxy resin laminated plate - Google Patents

Abstract

PURPOSE:To obtain a copper plated laminated epoxy plate superior in low dielectric, by a method wherein a prepreg to be obtained through a resin composition having epoxy resin represented by a formula I, a glycidyl etherification product of a halogen containing bisphenol compound respresented by a formula II and a curing agent for its components and a copper foil are laminate-molded. CONSTITUTION:A resin composition having epoxy resin represented by a formula I (in the formula, n represents mean repeating number, taking the numerical value of at least 0.2 and not exceeding 20. M, Q represent respectively independently halogen atom; 1-8C alkyl group or alkenyl group; 5-12C cycloalkyl group.), a glycidyl etherification product of a halogen containing bisphenol compound represented by a formula II (in the formula, R represents a hydrogen atom or a methyl group and Y, Y' represent a halogen atom.) and a resin curing agent for its component is infiltrated into a based and a prepreg is obtained. The same and a copper foil are laminate-molded and a copper plated epoxy resin laminated plate is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin copper clad laminate, and more particularly to an epoxy resin copper clad laminate excellent in low dielectric property.

[0002]

2. Description of the Related Art Among epoxy resins used for electric and electronic applications, as a material for a copper-clad laminate (printed wiring board), a combination of a bisphenol type epoxy resin and dicyandiamide has been mainly used. recent years,
With the increase in the number of copper-clad laminates, low dielectric properties of resins have been demanded mainly for the purpose of improving the signal speed. On the other hand, a method of combining a conventional epoxy resin with a low dielectric thermoplastic resin has been proposed. Invented. For example, a method of modifying with a reactive polybutadiene resin, a method of dispersing a powder of polytetrafluoroethylene resin, a method of using aramid fiber as a base material, and the like. In addition, there have been reported examples of using D-glass or quartz having a lower dielectric constant than conventional E-glass as a base material.

[0003]

However, in these conventional techniques, since the basic epoxy resin has a high dielectric constant, the proportion of the thermoplastic resin to be combined in order to achieve the desired dielectric constant becomes large. The heat resistance, dimensional stability, chemical resistance, etc., which are the characteristics of, are impaired. Further, when aramid fiber or quartz is used as the base material, there is a drawback that the wear of the drill is severe at the time of drilling the copper clad laminate, and when D-glass is used, there is no problem of the drill workability, but the manufacturing cost of the printed circuit board. Raises the problem. Therefore, a low-dielectric epoxy resin that can obtain a low-dielectric copper-clad laminate by itself has been desired. An object of the present invention is to provide a copper-clad laminate formed by using an epoxy resin composition having excellent heat resistance and low dielectric constant.

[0004]

Means for Solving the Problems As a result of continuous studies on the skeleton structure of an epoxy resin and various properties of a laminate to be obtained, the present inventors have found that a specific composition has excellent heat resistance and low dielectric property. The inventors have found that they also have the above, and have completed the present invention. That is, the present invention is as follows.
(1) (A) The following general formula (1)

[0005]

[Chemical 3] (In the formula, n represents an average number of repetitions and takes a value of 0.2 or more and 20 or less. M and Q are each independently a halogen atom; an alkyl group having 1 to 8 carbon atoms, an alkenyl group and an alkynyl group; A cycloalkyl group having 5 to 12 carbon atoms; an aryl group having 6 to 14 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group, an alkynyloxy group; a nitro group; a cyano group , I is an integer value of 0 or more and 4 or less, and j is an integer value of 0 or more and 3 or less).
(B) An epoxy resin copper-clad laminate obtained by laminating a prepreg obtained by dissolving a resin composition containing an epoxy resin curing agent as an essential component in an organic solvent and impregnating the base material with a copper foil.

(2) (A) The epoxy resin described in (1) above, and (B) the following general formula (2)

[Chemical 4] (In the formula, R represents a hydrogen atom or a methyl group, and two Rs may be the same or different from each other.
Y'is a halogen atom, and both may be the same or different. r and s are each independently an integer of 1 or more and 4 or less. ) Epoxy resin copper-clad laminate prepared in the same manner as in (1) above, using a resin composition containing a glycidyl ether compound of a halogen-containing bisphenol compound represented by (4) and (C) an epoxy resin curing agent as essential components. .

These inventions will be described in detail below. First, the dihydroxy compound represented by the following general formula (3), which is a raw material of the epoxy resin used in the present invention, will be described.

[0008]

[Chemical 5] (In the formula, n, M, Q, i, and j are defined in the same manner as in the general formula (1).) In the general formula (3), the value of n is a numerical value of 1 or more and 20 or less. However, it is preferably 1 or more and 10 or less in terms of the balance between the heat resistance of the compound and the low viscosity involved in the operability. The synthetic method of the dihydroxy compound of the general formula (3) includes the following general formula (4)

[0009]

[Chemical 6] (In the formula, M and i are defined in the same manner as in the general formula (3) above), and the phenol (a) represented by the following general formula (5).

[0010]

[Chemical 7] (In the formula, Q and j are defined in the same manner as in the general formula (3). Z ₁ and Z ₂ are

[0011]

[Chemical 8] Alternatively,

[0012]

[Chemical 9] However, Z ₁ and Z ₂ may be the same or different from each other. ) The compound (b) represented by the formula (2) is reacted in a suitable organic solvent in the presence of an acid catalyst while removing generated water, and then excess phenols and solvents are removed by neutralization, washing with water, and reduced pressure. However, the method is not limited to this.

The phenols (a) represented by the general formula (4) have one phenolic hydroxyl group and, for example, phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol. , Isobutylphenol, t
-Butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-
Various alkylphenols represented by t-butylphenol, di-t-amylphenol, etc. o-, m-, p-
Isomers: various o-, m of alkenyl or alkynylphenol represented by vinylphenol, allylphenol, propenylphenol, ethynylphenol, etc.
-, P-isomer; various o-, m-, p of alkoxy, alkenyloxy or alkynyloxyphenol represented by methoxyphenol, ethoxyphenol, allyloxyphenol, propargyloxyphenol, etc.
-Isomer; cycloalkylphenol represented by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, or halogen-substituted phenol represented by chlorophenol, dichlorophenol, bromophenol, dibromophenol; nitrophenol, cyanophenol, Examples thereof include substituted phenols such as arylphenol and aralkylphenol, and preferably 2,6-xylenol and 2-t.
-Butyl-5-methylphenol, 2-t-butyl-4
-Methylphenol, 2,4-di (t-butyl) phenol, 2,4-di (t-amyl) phenol, 2-cyclohexyl-5-methylphenol, 2-t-butylphenol, 2-sec-butylphenol, 2 -(T-
Amyl) phenol, 2-cyclohexylphenol and the like.

Specific examples of the compound (b) represented by the general formula (5) include diisopropenylbenzene, bis (α-hydroxyisopropyl) benzene and 1-isopropenyl-3-α-hydroxyisopropylbenzene. ,
Examples of the compounds include 1-isopropenyl-2-α-hydroxyisopropylbenzene, 1-isopropenyl-4-α-hydroxyisopropylbenzene and aromatic nucleus-substituted derivatives thereof, but from the viewpoint of economy,
m-Diisopropenylbenzene, p-diisopropenylbenzene, m-bis (α-hydroxyisopropyl) benzene and p-bis (α-hydroxyisopropyl) benzene are preferably used.

As the acid catalyst used for synthesizing the dihydroxy compound represented by the general formula (3), known ones are used. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and polyphosphoric acid, organic acids such as toluenesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid and thioglycolic acid, BF ₃ ether complex, BF ₃ phenol complex, Lewis acids such as aluminum chloride and zinc chloride, acid clay,
Examples thereof include solid acids such as silica-alumina and zeolite, heteropolyhydrochloric acid, acidic ion exchange resins, and the like, but toluenesulfonic acid, acid clay and acidic ion exchange resins are preferable.

The conditions for synthesizing the dihydroxy compound of the general formula (3) include a molar ratio of the phenol (a) to the compound (b) in the range of 0.1 to 10.0.
To obtain a preferable number of repeating units n, 0.5 to 5.0
Is preferred. The amount of the acid catalyst used can be selected from 0.1 to 50% by weight of the total weight of the phenols (a) and the compounds (b). However, in order to control the reaction rate and prevent the reaction time from becoming long, it is 5 -20% by weight is preferred. The reaction temperature may be in the range of 0 ° C to 300 ° C, but in order to suppress side reactions and make the reaction time appropriate, 50 to 200 ° C may be used.
C is preferred. The reaction time depends on the reaction temperature,
The reaction is not completed in a short time, and the decomposition reaction of the product may occur in a long time.
It is preferably carried out for 2 to 50 hours. In addition, the reaction can be carried out under reduced pressure so that the reaction proceeds smoothly.

When synthesizing a dihydroxy compound,
As an azeotropic dehydration solvent, a hydrocarbon solvent such as hexane, cyclohexane, heptane, benzene, toluene, xylene, etc., a halogenated hydrocarbon solvent such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, etc. Select from nitrated hydrocarbon solvents such as nitrobenzene and dinitrobenzene, ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and diphenyl ether, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. It is also possible to use a mixed solvent of these, but it is preferable to use toluene, chlorobenzene, nitrobenzene or methyl isobutyl ketone. Possible, this does not apply.

Further, it is possible to use the above-mentioned other solvents in combination, aprotic polar solvents such as dimethyl sulfoxide and N-methylpyrrolidone, amide solvents such as dimethylformamide and dimethylacetamide, methanol, Ethanol, propanol, isopropanol,
Examples thereof include alcohols such as butyl alcohol, but are not limited thereto.

The epoxy resin used in the present invention undergoes a diglycidyl etherification reaction by dehydrohalogenation of the dihydroxy compound of the general formula (3) and epihalohydrins in the presence of a basic compound such as caustic soda, caustic potash, and triethylamine. It can be obtained by a known method. Examples of the epihalohydrins include epichlorohydrin, epibromohydrin and the like, but from the economical aspect, epichlorohydrin is preferably used.

Specific examples of the glycidyl ether compound of the halogen-containing bisphenol compound represented by the general formula (2) used in the present invention include tetrabromobisphenol A, tetrachlorobisphenol A, tetraiodobisphenol A and tetrabromobisphenol. F, tetrachlorobisphenol F, tribromobisphenol A, 2,2'-dibromobisphenol A and the like are each glycidyl etherified, but tetrabromobisphenol A from the viewpoint of economical efficiency and imparting efficient flame retardancy. The glycidyl ether of is preferably used.

Regarding the usage ratio of the glycidyl ether compound of the halogen-containing bisphenol compound in the resin composition used in the present invention, the quantitative ratio of the halogen atoms contained can achieve V-0 in the UL standard flame retardancy evaluation of the laminate. It is desirable to prepare it in such a range. For example, in the case of a bromine atom, it is desirable to determine the use ratio of this component so that the epoxy resin composition contains a bromine atom in an amount of 15 to 30% by weight.

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 and aromatic aldehydes, oligomers of adducts of phenols with unsaturated alicyclic compounds, xylylene-bonded oligomers of phenols, polyhydroxystyrene,
Polyhydric phenols such as polyhydroxy bromostyrene,
Examples include amine curing agents such as aromatic amines and aliphatic amines, acid anhydrides, dicyandiamide, hydrazide compounds, Lewis acid complexes and the like. Preferred are dicyandiamide and polyhydric phenols. Further, the content thereof is preferably 0.3 to 1.2 equivalents based on 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 phenol novolac, glycidyl ether of cresol novolac, glycidyl ether of brominated phenol novolac, unsaturated polyester resin, cyanate resin, maleimide resin, glycidyl modified polybutadiene,
Examples thereof include maleic anhydride-modified polyethylene. 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. Examples of the curing accelerator include imidazoles, tertiary amines and phosphorus compounds, examples of the flame retardant include antimony trioxide, aluminum hydroxide and red phosphorus, and examples of the surface treatment agent include silane coupling agents.

The copper-clad laminate of the present invention can be prepared by a known method. That is, by impregnating a base material with a resin varnish obtained by dissolving the epoxy resin composition of the present invention in an organic solvent, heat-treating the prepreg and then forming a prepreg and a copper foil by laminating and heat-molding a copper-clad laminate. is there. 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, alone or in a mixture of two or more. It The base material to be impregnated with the resin varnish is a woven cloth made of inorganic fibers such as glass fibers, polyester fibers, polyamide fibers, or organic fibers, or a non-woven fabric, mat, paper or the like, and these may be used alone or in combination.

The heat treatment conditions for the prepreg are the solvent used,
Although it is appropriately selected depending on the type and amount of the added catalyst and various additives, it is usually carried out 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..

[0027]

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. In addition, hydrolyzable chlorine means that the epoxy resin is dissolved in dioxane, an alcohol solution of potassium hydroxide is added, and chlorine ions desorbed when heated at reflux for 30 minutes are back-titrated with an aqueous solution of silver nitrate. Is expressed as a weight percentage.

Synthesis Example 1 This synthesis example relates to a process for producing a dihydroxy compound which is a raw material of the epoxy resin of the present invention. 54-g of 2,6-xylenol was placed in a 2-liter 4-neck round bottom flask equipped with a drainage tube equipped with a thermometer, a stirrer, and a reflux condenser.
(4.5 mol), m-bis (α-hydroxyisopropyl)
Benzene 291.0 g (1.5 mol), toluene 840 g, acid clay 84
Charge g, raise the temperature to 110 ° C, and hold for 8 hours while azeotropically removing water. Concentration under reduced pressure gave 308 g of a resinous solid. Softening point is 85 ℃, OH equivalent is 381g
It was / eq. By infrared absorption spectrum measurement, absorption derived from the indane structure (2960,1485,1460,1440,740 cm ^-1 ) and
Absorption of OH groups (3600-3200 cm ^--1 ) was confirmed. Furthermore, it was confirmed to be the target by mass spectrometry and nuclear magnetic resonance spectrum measurement. This compound is a compound in which M is a methyl group, i = 2, j = 0, and n = 2.3 in the general formula (3).

Synthesis Example 2 This synthesis example relates to a process for producing the epoxy resin used in the present invention from the dihydroxy compound obtained in Synthesis Example 1. 60.0 g of the dihydroxy compound obtained in Synthesis Example 1
(0.157 moleq), epichlorohydrin 102.0 g (1.1 mol),
51.0 g of dimethyl sulfoxide was charged into a 1 liter 4-necked flat bottom flask equipped with a thermometer, a stirrer and a condenser with a separation tube, and 48.6% under the condition of 51 ° C and 42 torr.
Add 13.0 g (0.148 mol) of aqueous caustic soda solution over 5 hours. During this period, while maintaining the temperature at 51 ° 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, 59.6 g of an epoxy compound was obtained. The epoxy equivalent and hydrolyzable chlorine of the thus obtained epoxy compound were 495 g / eq and 160 ppm, respectively.
As a result of infrared absorption spectrum measurement, absorption of phenolic OH
3200-3500cm ^-1 disappeared, epoxide absorption 1220, 910c
It was confirmed to have an absorption of m ^-1 .

Example 1 Epoxy resin obtained in Synthesis Example 2 and diglycidyl ether of tetrabromobisphenol A (trade name: Sumiepoxy ESB-400, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 403 g)
/ eq), dicyandiamide and 2-ethyl-4-methylimidazole 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 give a uniform resin varnish. A glass cloth (trade name: KS-1600S962LP, manufactured by Kanebo Co., Ltd.) was impregnated with the varnish and treated with a hot air dryer at 150 ° C. for 5 to 10 minutes to obtain a prepreg. 5 sheets of prepreg and copper foil (TSTO treated 35μ thick, Furukawa Circuit Foil Co., Ltd.) are piled up and 170 ℃ ×
50 kg / cm ² × 120 minutes heat press molding was performed to obtain a 1 mm thick copper-clad laminate. Copper foil peeling strength and solder heat resistance of laminated board
It was 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 loss tangent at room temperature of 1 MHz are 42, manufactured by Yokogawa Hewlett-Packard Co., Ltd.
Using a 75A Multi-Frequency LCR meter, the value of dielectric constant was calculated from the capacitance of the sample. The measurement results are shown in Table 1.

Example 2 A phenol novolak resin (trade name: Tamanor 758, manufactured by Arakawa Chemical Industry Co., Ltd.) was blended in place of the dicyandiamide of Example 1 at a ratio shown in Table 1, and methyl ethyl ketone alone was used as a solvent. The same operation as in Example 1 was carried out to obtain a copper-clad laminate having a thickness of 1 mm. The physical properties of the laminated plate were also measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Example 3 Instead of the dicyandiamide of Example 1, a phenol-added polybutadiene resin (trade name PP-700-300, manufactured by Nippon Oil Co., Ltd.) was blended in a ratio shown in Table 1, and only methyl ethyl ketone was used as a solvent. A copper-clad laminate having a thickness of 1 mm was obtained in the same manner as in Example 1 except for the above. The physical properties of the laminated plate were also measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Example 4 A phenol-dicyclopentadiene resin (trade name DPP-600M, manufactured by Nippon Oil Co., Ltd.) was blended in the ratio shown in Table 1 in place of the dicyandiamide of Example 1, and only methyl ethyl ketone was used as a solvent. A copper-clad laminate having a thickness of 1 mm was obtained in the same manner as in Example 1 except for the above. The physical properties of the laminated plate were also measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Example 5 The epoxy resin of Synthesis Example 2 and brominated polyhydroxystyrene (trade name Marukaka Linker MB, manufactured by Maruzen Petrochemical Co., Ltd.) were blended at the ratio shown in Table 1, and only methyl ethyl ketone was used as a solvent. A copper-clad laminate having a thickness of 1 mm was obtained in the same manner as in Example 1 except for the above. The physical properties of the laminated plate were also measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Comparative Example 1 Epoxy resin with brominated epoxy resin (Sumitomo Chemical Co., Ltd. product name Sumiepoxy ESB-500, epoxy equivalent)
472g / eq) and cresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd. product name Sumiepoxy ESCN-22)
Dicyandiamide and 2-ethyl-4-methylimidazole were mixed at a ratio shown in Table 1 using 0 and an epoxy equivalent of 215 g / eq) 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-1600S)
962LP, manufactured by Kanebo Co., Ltd., and dried in a hot air dryer at 150 ° C.
It was treated for 5 to 10 minutes to obtain a prepreg. Five prepregs and copper foil (TSTO treated 35 μm thick, Furukawa Circuit Foil Co., Ltd.)
Manufactured by the above method and heat-pressed at 160 ° C. × 50 kg / cm ² × 90 minutes to obtain a copper-clad laminate having a thickness of 1 mm. The physical properties of the laminate were measured in the same manner as in Example 1 and the results are shown in Table 1.

[0036]

[Table 1]

[0037]

The cured resin of the epoxy resin composition of the present invention is excellent in heat resistance and has a low dielectric constant, and the copper-clad laminate molded using the same has excellent physical properties and is therefore suitable for high-speed arithmetic processing. Suitable for multilayer printed wiring boards.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shinichiro Kitayama 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. (A) The following general formula (1): (In the formula, n represents an average number of repetitions and takes a value of 0.2 or more and 20 or less. M and Q are each independently a halogen atom; an alkyl group having 1 to 8 carbon atoms, an alkenyl group and an alkynyl group; A cycloalkyl group having 5 to 12 carbon atoms; an aryl group having 6 to 14 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group, an alkynyloxy group; a nitro group; a cyano group , I is an integer value of 0 or more and 4 or less, and j is an integer value of 0 or more and 3 or less).
(B) An epoxy resin copper-clad laminate obtained by laminating a prepreg obtained by dissolving a resin composition containing an epoxy resin curing agent as an essential component in an organic solvent and impregnating the base material with a copper foil. 2. The epoxy resin according to claim 1 (A),
(B) The following general formula (2): (In the formula, R represents a hydrogen atom or a methyl group, and two Rs may be the same or different from each other.
Y'is a halogen atom, and both may be the same or different. r and s are each independently an integer of 1 or more and 4 or less. ) A prepreg and a copper foil obtained by dissolving a resin composition containing a glycidyl ether compound of a halogen-containing bisphenol compound represented by (4) and an epoxy resin curing agent (C) as an essential component in an organic solvent and impregnating the base material. An epoxy resin copper-clad laminate formed by laminating and molding.