JP2005314524A - Resin composition, prepreg and laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of providing a laminated sheet having excellent heat resistance, small coefficient of linear expansion in the thickness direction and good adhesiveness to a conductor circuit and a prepreg and a laminated sheet using the resin composition. <P>SOLUTION: The resin composition is used for forming the sheet-like prepreg by impregnating the composition into a substrate. The resin composition comprises an epoxy resin containing a dicyclopentadiene type epoxy resin, dicyandiamide and an aromatic amino compound having an electron-attracting group in the molecule. The prepreg is obtained by impregnating the resin composition into the substrate. The laminated sheet is obtained by molding one or more sheets of prepreg. <P>COPYRIGHT: (C)2006,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 (for example, see Patent Document 1). However, on the other hand, dicyclopentadiene type epoxy resins have a drawback of poor adhesion to conductor circuit metals.

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, dicyandiamide, and an aromatic amino compound having an electron withdrawing group in the molecule.
(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 the above (1) or (2), wherein the aromatic amino compound containing an electron withdrawing group in the molecule is 4,4′-diaminodiphenyl sulfone.
(4) The resin composition according to the above (1) or (2), wherein the aromatic amino compound containing an electron withdrawing group in the molecule is 3,3′-diaminodiphenyl sulfone.
(5) A prepreg obtained by impregnating a base material with the resin composition according to any one of (1) to (4).
(6) A laminate obtained by molding one or more prepregs according to (5) above.

  The present invention relates to a resin composition containing an epoxy resin containing a dicyclopentadiene type epoxy resin, dicyandiamide, and an aromatic amino compound having an electron withdrawing group in the molecule, and a prepreg and a laminate using the resin composition Therefore, it is possible to obtain a laminate having sufficient heat resistance, low linear expansion coefficient, and adhesion as compared with the conventional one.

The resin composition of the present invention is a resin composition used for forming a sheet-like prepreg by impregnating a substrate, an epoxy resin containing a dicyclopentadiene type epoxy resin, dicyandiamide, and an electron in the molecule. It contains an aromatic amino compound having an attractive group.
Moreover, the prepreg of the present invention is characterized in that a base material is impregnated with the above-mentioned resin composition.
The laminate of the present invention is characterized in that it is formed by molding one or more of the above 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, the heat resistance of a laminated board can be improved and 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.

  Although content of the said dicyclopentadiene type epoxy resin is not specifically limited, 60 to 90 weight% of the whole epoxy resin is preferable, and 70 to 80 weight% is especially preferable. When the content of the dicyclopentadiene type epoxy resin is less than the lower limit, the effect of improving the heat resistance may be lowered, and when the content exceeds the upper limit, the adhesion may be lowered.

  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 dicyandiamide. Thereby, adhesiveness can be improved, maintaining heat resistance.

  When dicyandiamide is used as a curing agent for an epoxy resin, the glass transition point of the cured epoxy resin is increased. Moreover, since nitrogen atoms are contained in dicyandiamide, adhesion is improved.

  However, dicyandiamide has poor solubility in epoxy resins, particularly dicyclopentadiene type epoxy resins. For this reason, when dicyandiamide necessary for sufficiently curing the dicyclopentadiene epoxy resin is added, dicyandiamide is precipitated in the resin composition, and unreacted dicyandiamide remains in the laminate, resulting in deterioration of heat resistance. There's a problem. Further, the amount of dicyandiamide that can be dissolved in the dicyclopentadiene epoxy resin has a problem that the curing is insufficient and the heat resistance is deteriorated.

On the other hand, the resin composition of the present invention is characterized by using an aromatic amino compound having an electron withdrawing group in the molecule together with dicyandiamide. Thereby, adhesiveness can be provided, without reducing heat resistance.
In the resin composition of the present invention, since an aromatic amino compound having an electron withdrawing group in the molecule is used together with dicyandiamide, an epoxy resin containing a dicyclopentadiene type epoxy resin (hereinafter simply referred to as “epoxy resin”) is used as the dicyandiamide. Can be used in an amount sufficient to dissolve. Thereby, the heat resistant fall by unreacted dicyandiamide depositing can be prevented.
Moreover, since the aromatic amino compound which has an electron withdrawing group in a molecule | numerator can advance hardening reaction of an epoxy resin by the amino group, it can provide sufficient heat resistance.
Furthermore, since the aromatic amino compound having an electron withdrawing group in the molecule has a slower curing reaction rate with respect to the epoxy resin than dicyandiamide, the viscosity of the resin composition is difficult to increase during the resin curing process. Thereby, the compounded dicyandiamide can be efficiently reacted with the epoxy resin without substantially reducing the solubility of dicyandiamide in the epoxy resin.
Thus, the resin composition of the present invention has the above-mentioned synergistic effect due to the combined use of both dicyandiamide and the aromatic amino compound having an electron withdrawing group in the molecule. It also has. Even when a dicyclopentadiene-type epoxy resin having poor solubility of dicyandiamide is used, high adhesion and heat resistance can be imparted to the laminate together with its low linear expansion.

The content of dicyandiamide is not particularly limited, but is preferably 1.5 to 3.5 parts by weight, particularly preferably 2.0 to 3.0 parts by weight with respect to 100 parts by weight of the epoxy resin.
If the content is less than the lower limit, the adhesion may be reduced, and if the content exceeds the upper limit, dicyandiamide may precipitate and heat resistance may be reduced.

The aromatic amino compound having an electron withdrawing group in the molecule is not particularly limited. For example, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone 4,4′-diaminostilbene-2,2′-disulfonic acid, 3,3′-dimethyl-4,4′-diaminobiphenyl-6,6′-disulfonic acid, o-toluidine disulfonic acid, 4,4 ′ -Diaminobenzophenone, 4,4'-diamino-3,3'-dicyanodiphenylmethane and the like.
Among these, 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone are preferable because they have good solubility in epoxy resins and do not inhibit the curing of dicyandiamide.
Here, examples of the electron withdrawing group in the aromatic amino compound having an electron withdrawing group in the molecule include a sulfonyl group, a carbonyl group, and a cyano group.

Although content of the aromatic amino compound which has an electron withdrawing group in the said molecule | numerator is not specifically limited, 2-10 weight part is preferable with respect to 100 weight part of epoxy resins, and 3-8 weight part is especially preferable.
When the content is less than the lower limit, the epoxy resin is not sufficiently cured, and the heat resistance of the laminate may be lowered. On the other hand, when the upper limit is exceeded, the aromatic amino compound that cannot participate in the curing reaction increases, and the heat resistance may similarly decrease.

  The resin composition of the present invention contains, as essential components, an epoxy resin containing the above-described dicyclopentadiene type epoxy resin, dicyandiamide, and an aromatic amine compound containing an electron withdrawing group in the molecule. As long as it does not violate the above purpose, other resins, curing accelerators such as imidazole compounds, 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 of impregnating the substrate with the resin composition obtained in the present invention include, for example, a method in which a resin varnish is prepared by dissolving the resin composition in a solvent, 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 has good solubility in the resin composition, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include dimethylformamide and dimethylacetamide.
The solid content in the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved.
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, 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.
In the case of a single prepreg, a metal foil or film is stacked on both upper and lower surfaces or one surface.
Two or more prepregs can be laminated. 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 prepreg.
Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil.
Although the temperature to heat is not specifically limited, 120-220 degreeC is preferable and especially 150-200 degreeC is 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 75.5 parts by weight of dicyclopentadiene type epoxy resin (epoxy equivalent 270, HP-7200H manufactured by Dainippon Ink & Chemicals, Inc.), brominated bisphenol A type epoxy resin (epoxy equivalent 400, Dainippon Ink) 153) 24.5 parts by weight, 2.3 parts by weight of dicyandiamide, 7.4 parts by weight of 4,4′-diaminodiphenylsulfone, 0.1 part by weight of 2-methylimidazole, and non-volatile content A resin varnish was prepared to a concentration of 55% by weight.

(2) Production of prepreg Using the resin varnish described above, 80 parts by weight of the resin varnish is impregnated in solid content with respect to 100 parts by weight of the glass fabric (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) A prepreg having a resin content of 44.4% by weight was produced by drying in a drying oven 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)
A resin varnish was prepared in the same manner as in Example 1 except that the amount of dicyandiamide was 2.7 parts by weight and the amount of 4,4'-diaminodiphenylsulfone was 5.3 parts by weight. Got.

(Example 3)
A resin varnish was prepared in the same manner as in Example 1 except that the blending amount of dicyandiamide was 3.0 parts by weight and the blending amount of 4,4'-diaminodiphenylsulfone was 3.2 parts by weight. Got.

Example 4
A resin varnish was prepared in the same manner as in Example 1 except that 3,3′-diaminodiphenylsulfone was used as an aromatic amino compound containing an electron withdrawing group in the molecule, and a prepreg and a laminate were obtained. .

(Comparative Example 1)
A resin varnish was prepared in the same manner as in Example 1 except that an aromatic amino compound containing an electron withdrawing group in the molecule was not used, only dicyandiamide was used as a curing agent, and the blending amounts shown in Table 1 were used. And the laminated board was obtained.

(Comparative Example 2)
Example 1 except that the aromatic amino compound containing an electron withdrawing group in the molecule was not used, and 4,4′-diaminodiphenylmethane containing no electron withdrawing group was used, and the blending amounts shown in Table 1 were used. Similarly, a resin varnish was prepared to obtain a prepreg and a laminate.

(Comparative Example 3)
Instead of dicyclopentadiene epoxy resin, a cresol novolac type epoxy resin is used, an aromatic amino compound containing an electron withdrawing group is not used in the molecule, and 4,4′-diamino does not contain an electron withdrawing group A resin varnish was prepared in the same manner as in Example 1 except that diphenylmethane was used and the blending amounts shown in Table 1 were obtained, 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.

Notes to the table Raw material (1) dicyclopentadiene type epoxy resin (epoxy equivalent 270, trade name: Dainippon Ink & Chemicals, Inc. HP-7200H)
(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.)

2. Evaluation Method (1) Glass Transition Temperature The glass transition temperature was determined from the tan δ peak temperature by the 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 in accordance with 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 in accordance with JIS C 6481.

As is clear from the table, Examples 1 to 4 of the present invention contain an epoxy resin containing a dicyclopentadiene type epoxy resin, dicyandiamide, and an aromatic amino compound having an electron withdrawing group in the molecule. It was a laminated board using a resin composition, and was excellent in heat resistance, linear expansion coefficient in the thickness direction, and adhesion.
On the other hand, Comparative Example 1 used only dicyandiamide as a curing agent, but the solder heat resistance and adhesion were lowered. In Comparative Example 2, an aromatic amino compound not containing an electron withdrawing group was used, but the epoxy resin was not sufficiently cured and the solder heat resistance was lowered. Moreover, since the comparative example 3 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 miniaturization and weight reduction, and are suitable for laminates that require high heat resistance, low linear expansion coefficient, and adhesion, and printed wiring boards using the same. .

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, dicyandiamide, and an aromatic amino compound having an electron withdrawing group in the molecule. 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 or 2, wherein the aromatic amino compound containing an electron withdrawing group in the molecule is 4,4'-diaminodiphenylsulfone. The resin composition according to claim 1 or 2, wherein the aromatic amino compound containing an electron withdrawing group in the molecule is 3,3'-diaminodiphenylsulfone. 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.