JP2005225926A - Resin composition, prepreg and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition which can provide a laminate which is excellent in heat resistance, has a small coefficient of linear expansion and shows a good adhesion to a conductor circuit, and a prepreg using the same and the laminate. <P>SOLUTION: The resin composition is used for forming the sheet-form prepreg by impregnating a substrate with the resin composition. The resin composition contains an epoxy resin containing a dicyclopentadiene epoxy resin and a biguanide compound. The prepreg is obtained by impregnating the substrate with the resin composition. The laminate is obtained by molding at least one prepreg. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  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 downsized. There is an increasing demand for reduction in size and weight even in a laminated board on which electronic components such as LSI are mounted. In order to reduce the size and weight, it is necessary to reduce the width of the conductor circuit, reduce the through-hole diameter, and reduce the plating thickness. However, if the plating thickness is reduced, plating cracks may occur during thermal shock, and connection reliability may be reduced. For this reason, the laminated board is required to have heat resistance and to have a small linear expansion coefficient in the thickness direction.

  A laminate using a dicyclopentadiene type epoxy resin can achieve both heat resistance and a low linear expansion coefficient in the thickness direction (see, for example, Patent Document 1). However, on the other hand, the dicyclopentadiene type epoxy resin has a drawback of poor adhesion to the conductor circuit metal.

Japanese Patent Laid-Open No. 11-181052

  The present invention provides a resin composition having excellent heat resistance, a linear expansion coefficient in the thickness direction and a good adhesion to a conductor circuit, and a prepreg and a laminate using the resin composition Is to provide.

Such an object is achieved by the present invention described in the following (1) to (6).
(1) A resin composition used for impregnating a base material to form a sheet-like prepreg,
A resin composition comprising an epoxy resin containing a dicyclopentadiene type epoxy resin and a biguanide compound.
(2) The resin composition according to (1), wherein the content of the dicyclopentadiene type epoxy resin is 60 to 90% by weight of the whole epoxy resin.
(3) The resin composition according to any one of (1) to (2), wherein the biguanide compound is tolylbiguanide.
(4) The resin composition according to any one of (1) to (2), wherein the biguanide compound is phenyl biguanide.
(5) A prepreg obtained by impregnating a base material with the resin composition according to any one of (1) to (4).
(6) A laminate comprising one or more prepregs according to (5) above.

  The present invention is an epoxy resin containing a dicyclopentadiene type epoxy resin, a resin composition containing a biguanide compound, and a prepreg and laminate using the resin composition, and has excellent heat resistance and linear expansion in the thickness direction. A laminated board having a small coefficient and good adhesion to a conductor circuit can be obtained.

The resin composition of the present invention is a resin composition used for impregnating a base material to form a sheet-like prepreg, and includes an epoxy resin containing a dicyclopentadiene type epoxy resin and a biguanide compound. It is what.
Moreover, the prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition.
Moreover, the laminated board of the present invention is formed by molding one or more of the above-described prepregs.
First, the resin composition of the present invention will be described.

  The resin composition of the present invention contains a dicyclopentadiene type epoxy resin. Thereby, while being able to improve heat resistance, such as a resin composition, a linear expansion coefficient can be made low.

  Although it does not specifically limit as a dicyclopentadiene type epoxy resin used with the resin composition of this invention, The epoxy resin which has the dicyclopentadiene frame | skeleton represented by the following general formula can be used suitably.

  As the dicyclopentadiene type epoxy resin represented by the above general formula, it is preferable to use one having n (average value) = 0.2 to 4.0. Thereby, heat resistance and low water absorption can be expressed.

  In the resin composition of the present invention, the content of the dicyclopentadiene-type epoxy resin is not particularly limited, but is preferably 60 to 90% by weight, particularly preferably 70 to 80% by weight based on the total epoxy resin. If the content of the dicyclopentadiene type epoxy resin is less than the lower limit, the effect of improving the heat resistance may be reduced, and if the content exceeds the upper limit, the adhesion may be reduced.

  In addition, in the resin composition of this invention, although it does not specifically limit as epoxy resins other than the said dicyclopentadiene type epoxy resin, For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, etc. can be used. It is preferable to use a brominated epoxy resin as the epoxy resin because it can be made flame retardant without deteriorating the properties of the epoxy resin.

  The resin composition of the present invention contains a biguanide compound. Thereby, adhesiveness can be improved, maintaining the heat resistance of a resin composition.

A conventionally known epoxy resin curing agent is dicyandiamide. When dicyandiamide is used as a curing agent for an epoxy resin, the glass transition point of the cured epoxy resin is increased. Further, since nitrogen atoms are contained in dicyandiamide, adhesion is improved.
However, since dicyandiamide has poor solubility in epoxy resins, particularly dicyclopentadiene type epoxy resins, there is a problem that dicyandiamide precipitates in the resin composition and heat resistance deteriorates.

In contrast, the present inventors have found that these problems can be solved by using a biguanide compound.
The reason is that the biguanide compound is more soluble in epoxy resin than dicyandiamide, and the glass transition point of the cured epoxy resin is also high. Moreover, it is mentioned that nitrogen content is high. For this reason, even if it uses a dicyclopentadiene type epoxy resin, sufficient heat resistance and adhesiveness can be expressed.

  The biguanide compound is not particularly limited, and examples thereof include phenyl biguanide, tolyl biguanide, methyl biguanide, and ethyl biguanide. Among these, tolyl biguanide and phenyl biguanide are preferable from the viewpoint of thermal stability and versatility.

The content of the biguanide compound is not particularly limited, but is preferably 2 to 16 parts by weight, more preferably 4 to 8 parts by weight with respect to 100 parts by weight of the entire epoxy resin including the dicyclopentadiene type epoxy resin. is there.
When the biguanide compound content is less than the above lower limit, the epoxy resin may not be sufficiently cured, and the solder heat resistance of the cured product may be reduced. On the other hand, when the above upper limit is exceeded, the biguanide compound that cannot participate in the curing reaction increases, so that the solder heat resistance of the cured product may similarly decrease.

  The resin composition of the present invention contains an epoxy resin containing the above-mentioned dicyclopentadiene type epoxy resin and a biguanide compound as essential components, but other resins and curing accelerators are within the scope of the object of the present invention. , Coupling agents, and other components may be added.

Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.
Examples of the base material used in the prepreg of the present invention include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, and aromatic polyamide resins. And organic fiber base materials composed of organic fibers such as polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

  Examples of the method for impregnating the substrate with the resin composition obtained in the present invention include, for example, a method in which the resin composition is dissolved in a solvent to prepare a resin varnish, and the substrate is immersed in the resin varnish. The method of apply | coating a varnish to a base material, the method of spraying a resin varnish on a base material with a spray apparatus, etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating device can be used.

The solvent used in the resin varnish desirably exhibits good solubility in the resin composition of the present invention, but a poor solvent may be used within a range that does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include methyl ethyl ketone and cyclohexanone.
Although it does not specifically limit as solid content ratio in the said resin varnish, It is preferable that the solid content of the said resin composition is 40 to 80 weight%, and 50 to 65 weight% is especially preferable. Thereby, the impregnation property to the base material of a resin varnish can further be improved.
A prepreg can be obtained by impregnating the substrate with the resin varnish and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, a laminated board is demonstrated.
The laminate of the present invention is formed by molding at least one prepreg described above. This
A laminate having excellent heat resistance, a small linear expansion coefficient in the thickness direction, and good adhesion can be obtained.
When one prepreg is used, a metal foil or film is stacked on both upper and lower surfaces or one surface.
Also, two or more prepregs can be laminated and used. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs.
Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil or the like.
Although the temperature to heat here is not specifically limited, 120-220 degreeC is preferable and 150-200 degreeC is especially preferable.
Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.

(Example 1)
(1) Preparation of resin varnish
71.5 parts by weight of dicyclopentadiene type epoxy resin (epoxy equivalent 270, HP-7200H manufactured by Dainippon Ink and Chemicals), brominated bisphenol A type epoxy resin (epoxy equivalent 400, 153 manufactured by Dainippon Ink and Chemicals) 23 Methyl ethyl ketone was added to .3 parts by weight, tolylbiguanide 5.2 parts by weight, and 2-methylimidazole 0.1 parts by weight to prepare a resin varnish having a nonvolatile content concentration of 55% by weight.

(2) Production of prepreg Using the above resin varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of the resin varnish as a solid content. A prepreg having a resin content of 44.4% by weight was prepared by drying in a drying furnace at 150 ° C. for 5 minutes.

(3) Manufacture of laminated board Six sheets of the above prepreg are stacked, and an electrolytic copper foil with a thickness of 35 μm is stacked on the top and bottom, and the pressure is 4 MPa, the temperature is 200 ° C. for 120 minutes, and the temperature is 220 ° C. for 60 minutes. A double-sided copper clad laminate having a thickness of 1.2 mm was obtained.

(Example 2)
Implemented except that the amount of dicyclopentadiene type epoxy resin was 85.0 parts by weight, the amount of brominated bisphenol A type epoxy resin was 9.5 parts by weight, and the amount of tolylbiguanide was 5.4 parts by weight. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.

(Example 3)
Except for 57.1 parts by weight of dicyclopentadiene type epoxy resin, 38.0 parts by weight of brominated bisphenol A type epoxy resin, and 4.9 parts by weight of tolylbiguanide. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.

Example 4
The compounding amount of dicyclopentadiene type epoxy resin is 71.7 parts by weight, the compounding amount of brominated bisphenol A type epoxy resin is 23.3 parts by weight, phenylbiguanide is used as the biguanide compound, and the amount of compounding is 4.8 parts by weight. Except that, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg and a laminate.

(Comparative Example 1)
A resin varnish was prepared in the same manner as in Example 1 except that dicyandiamide was used in place of tolyl biguanide and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

(Comparative Example 2)
A resin varnish was prepared in the same manner as in Example 1 except that a cresol novolac type epoxy resin was used instead of the dicyclopentadiene epoxy resin and the blending amounts shown in Table 1 were used, and a prepreg and a laminate were obtained.

  The following evaluation was performed about the laminated board obtained by each Example and the comparative example. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Table 1.

(1) Glass transition temperature The glass transition temperature was determined from the peak temperature of tan δ by a viscoelastic method.

(2) Linear expansion coefficient The linear expansion coefficient in the thickness direction was measured by TMA (thermomechanical analysis) and showed an average value from 50 ° C to 150 ° C.

(3) Solder heat resistance The solder heat resistance was measured according to JIS C 6481. In the measurement, after performing a moisture absorption treatment for 2 hours after boiling, it was immersed in a solder bath at 260 ° C. for 120 seconds and then examined for abnormal appearance.

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

Notes to Table (1) Dicyclopentadiene type epoxy resin (epoxy equivalent 270, trade name: HP-7200H manufactured by Dainippon Ink & Chemicals, Inc.)
(2) Brominated bisphenol A type epoxy resin (epoxy equivalent 400, bromination rate 49%, trade name: Dainippon Ink & Chemicals, Inc. 153)
(3) Cresol novolac type epoxy resin (epoxy equivalent 210, trade name: N-690 manufactured by Dainippon Ink & Chemicals, Inc.)

  As is apparent from the table, Examples 1 to 4 were excellent in heat resistance, linear expansion coefficient in the thickness direction, and adhesion. On the other hand, Comparative Example 1 used dicyandiamide as a curing agent, but the solder heat resistance and adhesion decreased. Moreover, since the comparative example 2 did not use the dicyclopentadiene type epoxy resin, it resulted in a poor linear expansion coefficient in the thickness direction.

  The resin composition, prepreg, and laminate of the present invention can be adapted to reduction in size and weight, and are suitable for printed wiring boards that require high heat resistance, low linear expansion coefficient, and adhesion.

Claims (6)

A resin composition used for impregnating a base material to form a sheet-like prepreg,
A resin composition comprising an epoxy resin containing a dicyclopentadiene type epoxy resin and a biguanide compound. 2. The resin composition according to claim 1, wherein the content of the dicyclopentadiene type epoxy resin is 60 to 90% by weight of the whole epoxy resin. The resin composition according to claim 1, wherein the biguanide compound is tolyl biguanide. The resin composition according to claim 1, wherein the biguanide compound is phenyl biguanide. A prepreg obtained by impregnating a base material with the resin composition according to claim 1. A laminate obtained by molding one or more prepregs according to claim 5.