JP2003238681A - Resin composition, prepreg, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition, a prepreg, and a laminate excellent in heat resistance and dielectric properties at high frequencies. <P>SOLUTION: The resin composition is one used for forming a sheety prepreg by impregnation into a base and comprises a novolak cyanate resin and a bismaleimide compound. The prepreg is prepared by impregnating a base with the resin composition. The laminate is prepared by molding at least one above prepreg. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

In recent years, information processing equipment such as a notebook personal computer and a mobile phone has been required to operate at high speed, and the CPU clock frequency has been increasing. Therefore, a high signal propagation speed is required. Therefore, it is necessary that the printed board has a low dielectric constant and a low dielectric loss tangent in a high frequency region.

Cyanate resin is used as a resin having excellent heat resistance and dielectric properties. The cyanate resin has 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, in reality, there is a drawback that unreacted cyanate groups remain due to strain of the resin cured product and the dielectric properties at high frequencies are poor.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition, a prepreg and a laminated board which have excellent heat resistance and dielectric properties at high frequencies.

[0005]

Such an object is achieved by the present invention described in (1) to (9) below. (1) A resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising a novolac type cyanate resin and a bismaleimide compound. (2) The resin composition according to (1) above, wherein the content of the novolac type cyanate resin is 60 to 80 parts by weight based on the entire resin composition. (3) The resin composition according to the above (1) or (2), wherein the novolac type cyanate resin is represented by the following general formula (I).

[Chemical 2] (4) The bismaleimide compound is 2,2-bis [4-
The resin composition according to any one of (1) to (3) above, which is (4-maleimidophenoxy) -phenyl] propane. (5) The bismaleimide compound is bis (3-ethyl-
The resin composition according to any one of (1) to (3) above, which is 5-methyl-4-maleimidophenyl) methane. (6) The resin composition according to any one of (1) to (5) above, wherein the content of the bismaleimide compound is 10 to 40 parts by weight based on the entire resin composition. (7) A prepreg obtained by impregnating a substrate with the resin composition according to any one of (1) to (6) above. (8) A laminate obtained by molding at least one prepreg according to (7) above.

[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 is characterized by containing a novolac type cyanate resin and a bismaleimide compound. is there. The prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition. The laminated board of the present invention is characterized by being formed by molding one or more of the above-mentioned prepregs.

The resin composition of the present invention will be described below. The resin composition of the present invention contains a novolac type cyanate resin. This can improve the heat resistance and dielectric properties of the resin composition. The cyanate resin includes a bisphenol type cyanate resin and a novolac type cyanate resin, and the novolac type cyanate resin is particularly used in the present invention. By using a novolac type cyanate resin and a bismaleimide compound described below in combination, a resin composition using a bisphenol type cyanate resin and a low water absorption, which was not obtained in a resin composition of a novolac type cyanate resin alone, have a solder heat resistance. Is something that can be achieved. The novolac type cyanate resin used in the present invention can be obtained, for example, by reacting a novolac resin and a cyanogen halide compound with heating.

The novolac type cyanate resin used in the present invention is not particularly limited, but those represented by the following general formula (I) are preferable.

[Chemical 3] The repeating unit n in the general formula (I) is not particularly limited, but is preferably 1 to 10 and preferably 1 to 7.
When n is less than the lower limit value, the novolac type cyanate resin is likely to be crystallized, and the solubility in a general-purpose solvent is relatively lowered, which may reduce workability. The solubility may decrease.

The content of the novolac type cyanate resin is not particularly limited, but it is 6 per 100 parts by weight of the resin component.
0 to 90 parts by weight is preferable, and 70 to 80 parts by weight is particularly preferable. If the content is less than the lower limit, the effect of improving heat resistance may be reduced, and if the content exceeds the upper limit, the adhesion may be reduced.

The resin composition of the present invention contains a bismaleimide compound, which makes it possible, in particular, to be 1 GHz to 10 GHz.
It is possible to improve the dielectric characteristics in a high frequency band such as. Examples of the bismaleimide compound include N,
N '-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 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 bis Examples include maleimide. Among these, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane or 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane is preferable.
Thereby, the water absorption of the resin composition can be further reduced.

The content of the bismaleimide compound is not particularly limited, but is 10 to 4 in 100 parts by weight of the resin component.
0 parts by weight is preferable, and 20 to 30 parts by weight is particularly preferable. If the content is less than the lower limit, the effect of improving the dielectric properties at high frequencies may be reduced, and if it exceeds the upper limit, the adhesion may be reduced.

As described above, the novolac type cyanate resin produces a triazine ring by the curing reaction. However, the triazine ring has excellent symmetry and therefore has small polarization and excellent dielectric characteristics. Moreover, since the crosslink density is high, the glass transition temperature is high and the heat resistance is excellent. However, the novolac type cyanate resin has a drawback that strain is generated at the time of curing due to its high crosslink density and unreacted cyanate groups remain, resulting in poor dielectric properties at high frequencies. In the present invention, in order to solve this problem, a novolac type cyanate resin is used in combination with a bismaleimide compound. The bismaleimide compound has excellent dielectric properties at high frequencies. Further, the double bond of maleimide reacts with the cyanate group, so that it can be incorporated into the resin skeleton, and the unreacted cyanate group can be completely reacted. Further, since the bismaleimide compound has excellent heat resistance, it does not lower the heat resistance of the novolac type cyanate resin.

The resin composition of the present invention contains the above-mentioned novolac type cyanate resin and the bismaleimide compound as essential components, but other resins, curing accelerators and coupling agents are used within the range not deviating from the object of the present invention. The flame retardant and other components may be added. When a brominated epoxy resin is used as the flame retardant, the epoxy group and the cyanate group react with each other and the flame retardant can be incorporated into the resin skeleton, which is preferable because the characteristics of the resin are not deteriorated.

Next, the prepreg will be described. The prepreg of the present invention is obtained by impregnating a substrate with the above resin composition. This makes it possible to obtain a prepreg having excellent heat resistance and dielectric properties (particularly dielectric properties in a high frequency band). As the substrate used in the present invention, glass fiber cloth, glass fiber base material such as glass non-woven cloth, or inorganic fiber base material such as fiber cloth or non-woven cloth containing an inorganic compound other than glass as a component, aromatic polyamide resin, polyamide resin Examples of the organic fiber base material include organic fibers such as aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these substrates, glass fiber materials represented by glass woven cloth are preferable in terms of strength and water absorption.

Examples of the method of impregnating the substrate with the resin composition obtained in the present invention include a method of impregnating the substrate with 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 allows
The impregnating property of the resin composition on the substrate can be improved. When impregnating the base material with 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 and dimethylformamide.
The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 40 to 80 parts by weight, and particularly preferably 50 to 65 parts by weight. This can further improve the impregnation property of the resin varnish into the base material. The base material is impregnated with the resin composition at a predetermined temperature, for example, 80 to 200 ° C.
It is possible to obtain a prepreg by drying the prepreg.

Next, the laminated plate will be described. The laminated plate of the present invention is formed by molding one or more of the above prepregs. This makes it possible to obtain a laminate having excellent heat resistance and dielectric properties (dielectric properties in a high frequency band). When using one prepreg, lay metal foil or film on the top or bottom or on one side. It is also possible to stack two or more prepregs. When laminating two or more prepregs, a metal foil or film is 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 stack of the prepreg and the metal foil. The heating temperature is not particularly limited, but is preferably 120 to 220 ° C., and particularly 1
50-200 degreeC is preferable. The pressure for heating 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 resin varnish Novolac type cyanate resin (PT-60 manufactured by Lonza)
70 parts by weight, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI manufactured by KAI KASEI Co., Ltd.)
-80) 30 parts by weight, dimethylformamide was added to 0.08 parts by weight of cobalt acetylacetonate, and the varnish was adjusted 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 prepregs are stacked, and electrolytic copper foils having a thickness of 35 μm are stacked on top and bottom, and pressure is 40 kgf / cm ² , temperature is 200 ° C.
And pressure-molded for 120 minutes at 220 ° C. for 60 minutes to obtain a double-sided copper clad laminate having a thickness of 1.2 mm.

Example 2 The procedure of Example 1 was repeated, except that the varnish was mixed as follows. 80 parts by weight of novolac type cyanate resin (PT-60 manufactured by Lonza),
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KI Kasei) was added to 2
It was 0 part by weight.

Example 3 The procedure of Example 1 was repeated, except that the varnish was mixed as follows. 65 parts by weight of novolac type cyanate resin (PT-60 manufactured by Lonza),
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KI Kasei Co., Ltd.) was added to 3 parts.
It was 5 parts by weight.

(Example 4) The procedure of Example 1 was repeated, except that the varnish was mixed as follows. 85 parts by weight of novolac type cyanate resin (PT-60 manufactured by Lonza Co., Ltd.),
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (BMI-80 manufactured by KI KASEI CO., LTD.) Was added to 1 part.
It was 5 parts by weight.

(Example 5) The same as Example 1 except that bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 manufactured by Kei Kasei Co., Ltd.) was used as the bismaleimide compound. did.

Example 6 The procedure of Example 1 was repeated, except that N, N ′-(4,4′-diphenylmethane) bismaleimide (BMI-H manufactured by Kei Kasei Co., Ltd.) was used as the bismaleimide compound. .

Comparative Example 1 The procedure of Example 1 was repeated, except that the bismaleimide compound was not used and 100 parts by weight of the novolac type cyanate resin was used.

Comparative Example 2 Instead of the bismaleimide compound, a bisphenol A epoxy resin (epoxy equivalent 4
75, product name: 1001 manufactured by Japan Epoxy Resins Co., Ltd.)
Same as Example 1 except that was used.

Comparative Example 3 The procedure of Example 1 was repeated except that a bisphenol type cyanate resin (B-40S manufactured by Ciba-Geigy) was used in place of the novolac type cyanate resin.

The following evaluations were carried out on the laminates obtained according to the above-mentioned Examples and Comparative Examples. The evaluation items are shown together with the method. The results obtained are shown in Table 1. The glass transition temperature sample was a 1.2 mm laminated plate, and the glass transition point was RDS-7700 manufactured by Rheometrics.
The measurement was performed at a temperature rising rate of 3 ° C./min and a frequency of 1 Hz.

Dielectric characteristic The measurement of frequency permittivity and dielectric loss tangent is JIS at 1 MHz.
It carried out according to C6481 and measured and calculated | required the electrostatic capacitance of frequency 1MHz. Also, the dielectric constant at a frequency of 1 GHz,
The dielectric loss tangent was measured by a triplate line resonator method using a network analyzer HP8510 manufactured by Agilent Technologies.

Solder heat resistance Solder heat resistance was measured according to JIS C6481. For the measurement, moisture absorption treatment was performed for 2 hours of boiling, and then, the presence or absence of abnormality in appearance was examined after immersion in a solder bath at 260 ° C. for 120 seconds.

Water absorption The water absorption rate was measured according to JIS C 6481.

Peel strength The peel strength was measured according to JIS C 6481.

[0034]

[Table 1] Note (1) Novolak type cyanate (softening point 60 ° C., product name: PT-60 manufactured by Lonza Co., Ltd.) (2) 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane (product name: BK manufactured by KAISEI CORPORATION
MI-80) (3) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (trade name: BMI- manufactured by Keisei Chemical Co., Ltd.)
70) (4) N, N '-(4,4'-diphenylmethane) bismaleimide (trade name: BMI-H manufactured by KAISEI KASEI CO., LTD.) (5) Cobalt acetylacetonate (6) Bisphenol A epoxy resin (epoxy equivalent 4
75, product name: 1001 manufactured by Japan Epoxy Resins Co., Ltd.)

As is apparent from the table, Examples 1 to 6 are
It had excellent heat resistance and dielectric properties, and had a low water absorption. Further, in Examples 1, 2 and 4, the peel strength was particularly excellent and the adhesion was improved.

[0036]

The heat-resistant resin composition of the present invention, when applied to a printed wiring board material, has high heat resistance, low dielectric constant and excellent water absorption. is doing. Therefore, in the future, it is intended to provide a resin composition which is most suitable for a printed circuit board which is in danger of small information processing.

Continued front page    F-term (reference) 4F072 AA04 AA07 AB04 AB05 AB06                       AB07 AB08 AB09 AB29 AD43                       AG03 AG12 AG16 AH02 AH24                       AH25 AH26 AH31 AK12 AK13                       AK20 AL13                 4J043 PA15 PA19 PB09 QB64 QC24                       RA33 RA47 SA13 TA73 UA121                       UA122 UA352 UB011 UB012                       UB132 WA07 XA19 ZA12                       ZA42 ZB50 ZB59

Claims (8)

[Claims] 1. A resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising a novolac type cyanate resin and a bismaleimide compound. 2. The resin composition according to claim 1, wherein the content of the novolac type cyanate resin is 60 to 90 parts by weight based on the entire resin composition. 3. The resin composition according to claim 1, wherein the novolac type cyanate resin is represented by the following general formula (I). [Chemical 1] 4. The bismaleimide compound is 2,2-
Bis [4- (4-maleimidophenoxy) -phenyl]
The resin composition according to any one of claims 1 to 3, which is propane. 5. The bismaleimide compound is bis (3
-Ethyl-5-methyl-4-maleimidophenyl) methane, The resin composition according to any one of claims 1 to 3. 6. The content of the bismaleimide compound is
The resin composition according to any one of claims 1 to 5, which is 10 to 40 parts by weight of the entire resin composition. 7. A prepreg obtained by impregnating a base material with the resin composition according to any one of claims 1 to 6. 8. A laminated board formed by molding at least one prepreg according to claim 7.