JP2003128765A - Heat-resistant resin composition, prepreg using the same and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has excellent heat resistance, dielectric characteristics and adhesiveness, to provide a prepreg, and to provide a laminate. SOLUTION: This resin composition which is impregnated into a substrate to form a sheet-like prepreg is characterized by containing a benzocyclobutene resin and/or its prepolymer, and a bismaleimide compound. The prepreg is characterized by impregnating the substrate with the resin composition. The laminate is characterized by laminating one or more prepreg and heating and pressurizing the laminate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, a prepreg and a laminate.

Information processing devices such as notebook personal computers and mobile phones are required to be miniaturized. LS
There is an increasing demand for downsizing and weight reduction in printed wiring boards on which electronic components such as I are mounted. To reduce the size and weight, it is necessary to reduce the wiring width and to reduce the through hole diameter and the plating thickness. If the plating thickness is made thin, cracks may occur during thermal shock, and heat resistance is required. At the same time, it is required to speed up these information processing crises, and the CPU clock frequency is increasing. Therefore, it is required to increase the signal propagation speed, and it is necessary to use a printed board having a low dielectric constant and a low dielectric loss tangent, which is advantageous for increasing the speed.

A benzocyclobutene resin is used as a resin having excellent heat resistance and dielectric properties (for example, Japanese Patent Laid-Open No. 2000-21872). The benzocyclobutene resin has very excellent dielectric properties because it does not generate a reactive group having a large polarization such as a hydroxyl group due to the curing reaction. However, since these polar groups are not present, there is a drawback that the adhesion to the copper foil is lacking. Elastomers such as polybutadiene are used together to supplement the adhesion, but these compounds have a large linear expansion coefficient and may cause plating cracks.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which is excellent in heat resistance, dielectric properties and adhesion when made into a prepreg. Another object of the present invention is to provide a prepreg excellent in heat resistance, dielectric properties and adhesion, and a laminated plate made of the prepreg.

[0005]

These objects are achieved by the present invention described in (1) to (7) below. (1) A resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising a benzocyclobutene resin and / or its prepolymer and a bismaleimide compound. Composition. (2) The resin composition according to (1) above, wherein the benzocyclobutene resin is represented by formula (I).

[Chemical 2] (3) The content of the benzocyclobutene resin is 40 to 80 parts by weight based on 100 parts by weight of the resin component (1).
Alternatively, the resin composition according to (2). (4) The bismaleimide compound is N, N ′-(4,
4'-diphenylmethane) bismaleimide, bis (3-
Any of the above (1) to (3), which is at least one selected from ethyl-5-methyl-4-maleimidophenyl) methane and 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane. The resin composition according to claim 1. (5) The resin composition according to any one of (1) to (4) above, wherein the content of the bismaleimide compound is 10 to 40 parts by weight in 100 parts by weight of the resin component. (6) A prepreg obtained by impregnating a substrate with the resin composition according to any one of (1) to (5) above. (7) A laminated board comprising one or more prepregs according to (6) above, which are heated and pressed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition, prepreg and laminate of the present invention will be described in detail below. The resin composition of the present invention is a resin composition used for forming a sheet-like prepreg by impregnating a base material, and contains a benzocyclobutene resin and / or its prepolymer and a bismaleimide compound. It is characterized by that. Further, the prepreg of the present invention is characterized in that a base material is impregnated with the above resin composition.
In addition, the laminated board of the present invention comprises one or two of the above prepregs.
It is characterized in that at least one sheet is superposed and heated and pressed.

First, the resin composition will be described. The resin composition of the present invention contains a benzocyclobutene resin and / or its prepolymer. Thereby, excellent heat resistance can be obtained. In addition, it can have excellent dielectric properties. The benzocyclobutene resin is considered to have excellent heat resistance because it has a rigid structure. In addition, the benzocyclobutene resin is considered to have excellent dielectric properties because polar groups such as hydroxyl groups that have large polarization are not generated by the curing reaction.

The benzocyclobutene resin is not particularly limited as long as it is a resin containing a cyclobutene skeleton. Among these, it is preferable to include a benzocyclobutene resin represented by the general formula (I). Thereby, the glass transition temperature can be increased and the resin characteristics after curing can be improved.

[Chemical 3] Further, a prepolymerized benzocyclobutene resin having such a general formula is also preferably used for adjusting moldability and fluidity. The prepolymerization is usually performed by heating and melting.

The content of the benzocyclobutene resin and / or the prepolymer thereof is preferably 40 to 80 parts by weight, more preferably 50 to 70 parts by weight, based on 100 parts by weight of the resin component. When the content of the benzocyclobutene resin or the like is less than the lower limit value, the effect of improving the dielectric properties may decrease, and when the content exceeds the upper limit value, the moldability may decrease.

The resin composition of the present invention contains a bismaleimide compound. This makes it possible to improve the adhesion between the prepreg and the metal foil when the prepreg made from the resin composition is heated and pressed to obtain a laminated plate. The bismaleimide compound has a low coefficient of linear expansion and has heat resistance, so that plating cracks do not occur. Further, since nitrogen and oxygen atoms are contained in the compound, it is considered that the adhesion with the metal foil can be improved. Furthermore, since the bismaleimide compound has a highly reactive double bond in the molecule, it can be copolymerized with the above-mentioned benzocyclobutene resin. Therefore, the adhesiveness can be improved without lowering the excellent heat resistance, dielectric properties and low water absorption of the benzocyclobutene resin.

Examples of the bismaleimide compound include N, N '-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2'-bis. [4- (4-maleimidophenoxy) phenyl] propane, N, N'-phenylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4'-diphenylpropane bismaleimide , N, N′-4,4′-diphenyl ether bismaleimide and the like. Among these, N, N '-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-
4-maleimidophenyl) methane, 2,2'-bis [4
At least one selected from-(4-maleimidophenoxy) phenyl] propane is preferable, and particularly 2,
2'-Bis [4- (4-maleimidophenoxy) phenyl] propane is preferred. Thereby, the adhesiveness and low water absorption of the resin composition and the prepreg can be further improved.

The content of the bismaleimide compound is preferably 10 to 40 parts by weight in 100 parts by weight of the resin component,
Particularly, 20 to 30 parts by weight is preferable. If the content is less than the lower limit, the effect of improving the adhesion may be reduced, and if it exceeds the upper limit, the water absorption may be reduced.

The resin composition of the present invention contains the above-mentioned benzocyclobutene resin and bismaleimide compound, but other resins, flame retardants, curing accelerators, coupling agents, Other components may be added.

Next, the prepreg will be described. The prepreg of the present invention is characterized in that a base material is impregnated with the above resin composition. This makes it possible to obtain a prepreg having excellent heat resistance, dielectric properties and adhesion. As the substrate, for example, glass woven fabric, glass non-woven fabric, glass fiber substrate such as glass paper, paper,
Examples thereof include woven and non-woven fabrics made of synthetic fibers such as aramid, polyester and fluororesin, woven fabrics, non-woven fabrics and mats made of metal fibers, carbon fibers, mineral fibers and the like.
You may use these base materials individually or in mixture. Of these, a glass fiber base material is preferable. This can improve the rigidity and dimensional stability of the prepreg.

The method of impregnating the base material with the resin composition includes, for example, a method of immersing the base material in a resin varnish, a method of coating with various coaters, and a method of spraying. Among these, the method of immersing the base material in the resin varnish is preferable. This can improve the impregnation property of the resin composition into the base material. When the base material is dipped in the resin varnish, ordinary impregnation coating equipment can be used.

The solvent used for the resin varnish preferably has good solubility in the resin composition, but a poor solvent may be used as long as it does not adversely affect the resin composition. Examples of the solvent exhibiting good solubility include methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone and the like. The solid content of the resin varnish is
Although not particularly limited, the solid content of the resin composition is 40 to 8
0% by weight is preferable, and 50 to 65% by weight is particularly preferable. This can further improve the impregnation property of the resin varnish into the base material. A prepreg can be obtained by impregnating the base material with the resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, the laminated plate will be described. The laminated board of the present invention is characterized in that one or more of the above-mentioned prepregs are superposed and heated and pressed.
This makes it possible to obtain a laminate having excellent heat resistance, dielectric properties and adhesion. In the case of one prepreg, metal foil or film is laminated on both upper and lower surfaces or one surface. Also, two or more prepregs can be laminated. When laminating two or more prepregs, metal foils or films are laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs. Next, a laminated plate can be obtained by heating and pressing a laminate of the prepreg and the metal foil or film. The heating temperature is not particularly limited, but is preferably 120 to 220 ° C., and particularly 15
0-200 degreeC is preferable. The pressure to be applied is
Although not particularly limited, 2 to 5 MPa is preferable, and 2.5 to 4 MPa is particularly preferable.

[0018]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. (Example 1) Preparation of varnish Divinylsiloxane-bisbenzocyclobutene (prepolymerized, weight average molecular weight 140,000, Cycloten XUR manufactured by Dow Chemical Co.) 70 parts by weight, bis (3-ethyl-5-methyl-4) -Maleimidophenyl)
Cyclohexanone was added to 30 parts by weight of methane (BMI-70 manufactured by KAI KASEI Co., Ltd.) to prepare a varnish so that the concentration of nonvolatile components was 55% by weight.

Preparation of prepreg Using the above-mentioned varnish, glass fiber cloth (thickness 0.18 m
m, manufactured by Nitto Boseki Co., Ltd.) and 80 parts by weight of the varnish solid content were impregnated and dried in a dryer oven at 150 ° C. for 5 minutes to prepare a prepreg having a resin content of 44.4%.

Preparation of Laminated Plate Six pieces of the above-mentioned prepregs were piled up, 35 μm thick electrolytic copper foils were piled up and down, pressure 40 kgf / cm ² , temperature 200
By heat and pressure molding at 120 ° C. for 120 minutes and then at 220 ° C. for 60 minutes, a double-sided copper clad laminate having a thickness of 1.2 mm was produced.

Example 2 Divinylsiloxane-bisbenzocyclobutene (prepolymerized, weight average molecular weight 140,000, Cycloten X manufactured by Dow Chemical Company)
60 parts by weight of UR, bis (3-ethyl-5-methyl-)
4-maleimidophenyl) methane (Kai Kasei B
Example 1 was repeated except that the amount of MI-70) was changed to 40 parts by weight.

Example 3 Divinylsiloxane-bisbenzocyclobutene (prepolymerized, weight average molecular weight 140,000, Cycloten X manufactured by Dow Chemical Company)
90 parts by weight of UR, bis (3-ethyl-5-methyl-)
4-maleimidophenyl) methane (Kai Kasei B
The same procedure as in Example 1 was carried out except that MI-70) was changed to 10 parts by weight.

Example 4 In place of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 manufactured by Kei Kasei Co.), 2,2'-bis [4- (4
Same as Example 1 except that -maleimidophenoxy) phenyl] propane was used.

Example 5 Divinylsiloxane-bisbenzocyclobutene (prepolymerized, weight average molecular weight 140,000, Cycloten X manufactured by Dow Chemical Co.)
40 parts by weight of UR, bis (3-ethyl-5-methyl-)
4-maleimidophenyl) methane (Kai Kasei B
MI-70) 40 parts by weight, brominated bisphenol A epoxy resin (bromination rate 50%, epoxy equivalent 40
0) The same as Example 1 except that 20 parts by weight was used.

Comparative Example 1 Divinylsiloxane-bisbenzocyclobutene (prepolymerized, weight average molecular weight 140,000, Cycloten X manufactured by Dow Chemical Co.)
UR) as 100 parts by weight, and bis (3-ethyl-5-
Example 1 except that methyl-4-maleimidophenyl) methane (BMI-70 manufactured by Keisei Co., Ltd.) was not used.
Same as.

Comparative Example 2 Instead of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 manufactured by Kei Kasei Co., Ltd.), polybutadiene (JSR) was used.
The same procedure as in Example 1 was carried out except that a product having a molecular weight of 100,000) was used.

(Performance Evaluation) Solder heat resistance, dielectric properties, water absorption coefficient, linear expansion coefficient and peel strength of the obtained laminated plate were measured. Solder heat resistance, peel strength and water absorption are J
It was measured according to IS C 6481. Regarding the solder heat resistance, after conducting a moisture absorption treatment for 2 hours of boiling, it was immersed in a solder bath at 260 ° C. for 120 seconds, and then examined for abnormal appearance. The dielectric constant and dielectric loss tangent were measured according to JIS C 6481, and the capacitance at a frequency of 1 MHz was measured. Regarding the linear expansion coefficient, the value from room temperature to the glass transition point was determined by the TMA method in the thickness direction of the laminated plate. The evaluation results are shown in Table 1.

[0028]

[Table 1] Notes to the table (1) Divinylsiloxane-bisbenzocyclobutene (prepolymerization: molecular weight 140000) (2) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (3) 2,2'-bis [ 4- (4-maleimidophenoxy) phenyl] propane (4) Brominated bisphenol A epoxy resin (bromination rate 50%, epoxy equivalent 400) (5) Polybutadiene (molecular weight 100000)

As is apparent from the table, the laminated plates obtained in Examples 1 to 5 were excellent in solder heat resistance, dielectric constant, dielectric loss tangent, peel strength and the like.

[0030]

According to the present invention, it is possible to obtain a resin composition which is excellent in heat resistance, dielectric properties and adhesion when formed into a prepreg. Further, according to the present invention, heat resistance,
It is possible to obtain a prepreg excellent in dielectric properties and adhesiveness and a laminated plate made of the prepreg. Further, when the benzocyclobutene resin has a specific content, it is possible to obtain a resin composition, a prepreg and a laminated board which are particularly excellent in low water absorption.

Claims (7)

[Claims] 1. A resin composition used for forming a sheet-like prepreg by impregnating a base material, which comprises a benzocyclobutene resin and / or a prepolymer thereof and a bismaleimide compound. Resin composition. 2. The resin composition according to claim 1, wherein the benzocyclobutene resin is represented by the formula (I). [Chemical 1] 3. The resin composition according to claim 1, wherein the content of the benzocyclobutene resin is 40 to 80 parts by weight based on 100 parts by weight of the resin component. 4. The bismaleimide compound is N, N ′.
Selected from-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane. The resin composition according to any one of claims 1 to 3, which is at least one kind. 5. The content of the bismaleimide compound is
The resin composition according to any one of claims 1 to 4, which is 10 to 40 parts by weight in 100 parts by weight of the resin component. 6. A prepreg obtained by impregnating a base material with the resin composition according to any one of claims 1 to 5. 7. A laminate comprising one or more of the prepregs according to claim 6 superposed and heated and pressed.