JPH07309996A - Resin composition for laminated plate and laminated plate formed using the same - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. for laminated plate excellent in shelf stability at room temp. in the form of a varnish, curability in a short laminating time, etc., by using predetermined amts. of a specific phenol-formaldehyde resin and a specific compd. CONSTITUTION:This resin compsn. comprises 100 pts.wt. phenol-formaldehyde resin contg. 60-90wt.%. drying oil (e.g. tung oil)-modified phenol-formaldehyde resin; and 0.1-20 pts.wt. compd. having a plurality of amine structures in the molecule thereof (e.g. 1-amino-4-methylpiperazine). Fiber sheet materials are impregnated with this resin compsn., dried, laminated on each other, and subjected to monolithic forming under heat and pressure to form a laminated plate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a fast-curing phenolic resin laminate, which has excellent stability near room temperature and excellent curability at high temperatures, and a laminate.

[0002]

2. Description of the Related Art Recently, consumer phenolic resin laminates and copper clad laminates used in insulating materials, especially in communication equipment and electronic equipment, are relatively ordinary temperature or near ordinary temperature from the viewpoint of automation of processing equipment and energy saving. It is required to have excellent punching workability. For this reason, as the resin for the laminated plate, a phenol-formaldehyde resin obtained by using various alkylphenols in combination with phenol and modified with a drying oil is usually used.

However, the modification with a drying oil reduces the reactivity of the phenol reacted with the drying oil at the ortho and para positions, and the steric hindrance due to the drying oil chain makes it difficult to form a crosslinked structure. The modified phenol-formaldehyde resin has a slow curing speed. Furthermore, in the modification with a drying oil, a polymer of the drying oil is produced, so that the chain length between crosslinks becomes long and the crosslink density also decreases. For this reason, the resin in the laminate is likely to be insufficiently cured in a short lamination molding time, and properties such as heat resistance, mechanical strength, electrical properties, and water resistance are deteriorated. Further, during punching, delamination and the like are likely to occur due to the low crosslink density. However, on the other hand, in order to improve the productivity, it is required that the desired performance be exhibited by heat molding for a short time. For this purpose, recently, there is a case (for example, Japanese Patent Laid-Open No. 50-84690) in which various kinds of catalysts are added to a varnish to enable hot molding for a short time. On the other hand, although the curability is improved, the resinification reaction proceeds even if it is left to stand near room temperature, resulting in poor impregnation of the resin into the laminated base material and the above-mentioned properties are deteriorated. Thus, it has been difficult to achieve both the storage stability of the varnish near room temperature and the rapid curing property at high temperature.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a problem that the conventional drying oil-modified phenol / formaldehyde resin has a slow curing rate, and that sufficient performance cannot be obtained by short-time heat molding, and it is highly reactive at high temperatures. However, it was made to solve the problem that there is no stability near room temperature, the purpose is to have excellent storage stability of varnish near room temperature and curability even for a short lamination molding time. The present invention provides a resin composition for a phenol resin laminate, which is excellent in punching workability, mechanical properties, electrical properties, and water resistance, and a laminate using the same.

[0005]

According to the present invention, 100 parts by weight of a phenol-formaldehyde resin containing 60 to 90% by weight of a drying oil-modified phenol-formaldehyde resin is mixed with a compound having a plurality of amine structures in the molecule. .
1 to 20 parts by weight of a resin composition for a laminated board, which is obtained by impregnating and drying the resin composition for a laminated board, laminating and laminating, and having the above-mentioned excellent properties. Is.

The compound having a plurality of amine structures in the molecule used in the present invention is specifically 2,5-
Dimethylpiperazine, 1,3-di (4-piperidyl) propane, 1,4-dimethylpiperazine, 4-aminomethylpiperidine, 1-amino-4-methylpiperazine, 1
-Hydroxyethylpiperazine, 1-aminoethylpiperazine and the like are mentioned, and it is necessary to use one or several of them in combination.

The dry oil-modified phenol-formaldehyde resin can be synthesized by reacting a dry oil with phenols in the presence of an acid catalyst, and further reacting formaldehyde with a base catalyst to form a resole. As the drying oil, tung oil, linseed oil, castor oil and the like are used, and as the phenols, alkylphenol having 1 to 20 carbon atoms such as phenol, cresol or nonylphenol is used.

An organic acid such as paratoluenesulfonic acid is used as the acid catalyst. Further, as the base catalyst for reacting the reaction product of the drying oil and the phenol with formaldehyde, ammonia water or amines such as triethylamine is used.

The laminated sheet of the present invention is prepared by dissolving a compound having a plurality of different amine structures in the molecule in an organic solvent and then adding it to a dry oil-modified phenol / formaldehyde resin to dissolve it into a varnish. It can be obtained by impregnating and drying the material, usually stacking 3 to 10 sheets, and heat-pressing.

The addition amount of the compound having a plurality of amine structures in the molecule to the phenol / formaldehyde resin is preferably 0.1 to 20 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the solid content of the phenol / formaldehyde resin. 20 parts by weight. If it is less than 0.1 part by weight, the effect of improving the curability is small, and if it exceeds 20 parts by weight, the storage stability of the varnish at around room temperature is lost, and the usable life of the prepreg becomes extremely short, which is industrial. The value is significantly reduced.

Further, in the present invention, the use of the flame retardant is not limited because the effect of the present invention is not impaired even when the flame retardant is added and mixed for imparting flame resistance.

[0013]

The phenol resin laminate obtained by the present invention has a short crosslinking rate due to an increase in the crosslinking rate due to the catalytic action of compounds having a plurality of different amine structures in the molecule contained in the resin component for varnish at high temperature. Since a sufficient crosslink density can be obtained even in time, it is considered that the curability is excellent and the punching workability, mechanical properties, electrical properties, and water resistance are good.

[0014]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Synthesis Example 1) 90 parts of a mixture of 1000 g of phenol, 840 g of tung oil and 1 g of paratoluenesulfonic acid.
The reaction was carried out at 0 ° C for 1 hour. Then, 15 g of 25% ammonia water was added to this to neutralize, and 37% formalin 150 was added.
0 g and 3 g of ethylenediamine were added and reacted at 100 ° C. for 3 hours, and then dehydrated under reduced pressure to give toluene 400
g, diluted with 800 g of methanol to give a resin content of 50
% Tung oil-modified phenol-formaldehyde resin (resin 1) was obtained.

(Synthesis Example 2) Phenol 1000 g, 37
% Formalin (1550 g) and triethylamine (80 g) were mixed and reacted at 70 ° C. for 3 hours, then dehydrated under reduced pressure, and 700 g of methanol was added to dilute the mixture to give a resin content of 5
A 0% low molecular weight phenol-formaldehyde resin (resin 2) was obtained.

(Example 1) Resins 1 and 2 obtained in Synthesis Examples 1 and 2 were mixed in an amount of 1000 g and 220 g, respectively, and then 100 parts by weight of the solid content of this varnish were mixed with a plurality of amine structures in the molecule. As a compound having 1-amino-4-
The varnish obtained by adding and mixing 2 parts by weight of methylpiperazine was impregnated into kraft paper and dried to obtain a prepreg having a total resin content of 50%.

Example 2 As a compound having a plurality of amine structures in the molecule, 4-aminomethylpiperidine was added and mixed in an amount of 3 parts by weight with respect to 100 parts by weight of the solid content of varnish, and the above-mentioned Example 1 was used. A prepreg having a total resin content of 50% was obtained in the same manner as in (1).

Example 3 As a compound having a plurality of amine structures in the molecule, 1-aminoethylpiperazine was added and mixed in an amount of 4 parts by weight with respect to 100 parts by weight of the solid content of the varnish, and the above-mentioned Example 1 was used. A prepreg having a total resin content of 50% was obtained in the same manner as in (1).

Example 4 As a compound having a plurality of amine structures in the molecule, 1-hydroxyethylpiperazine was added and mixed in an amount of 6 parts by weight with respect to 100 parts by weight of the solid content of the varnish. A prepreg having a total resin content of 50% was obtained in the same manner as in (1).

(Example 5) As a compound having a plurality of amine structures in the molecule, 2,5-dimethylpiperazine was added and mixed in an amount of 5 parts by weight based on 100 parts by weight of the solid content of the varnish. A prepreg having a total resin content of 50% was obtained in the same manner as in method 1.

Example 6 As the compound having a plurality of amine structures in the molecule, 1,4-dimethylpiperazine was added and mixed in an amount of 5 parts by weight with respect to 100 parts by weight of the solid content of the varnish, and the above examples were mixed. A prepreg having a total resin content of 50% was obtained in the same manner as in method 1.

Example 7 As a compound having a plurality of amine structures in the molecule, 1-aminoethylpiperazine was added and mixed in an amount of 0.5 part by weight with respect to 100 parts by weight of the solid content of varnish. A prepreg having a total resin content of 50% was obtained in the same manner as in the method of Example 1.

Example 8 As a compound having a plurality of amine structures in the molecule, 1-aminoethylpiperazine was added and mixed in an amount of 10 parts by weight with respect to 100 parts by weight of the solid content of varnish, and the above-mentioned Example 1 was used. A prepreg having a total resin content of 50% was obtained in the same manner as in (1).

Comparative Example 1 As a compound having a plurality of amine structures in the molecule, 1-aminoethylpiperazine was added and mixed in an amount of 21 parts by weight with respect to 100 parts by weight of the solid content of the varnish, and the above-mentioned Example 1 was used. A prepreg having a total resin content of 50% was obtained in the same manner as in (1).

Comparative Example 2 A prepreg having a total resin content of 50% was obtained in the same manner as in Example 1 except that a compound having a plurality of amine structures in the molecule was not added and mixed.

Comparative Example 3 Diaminodiphenylmethane having only a primary amine instead of a compound having a plurality of amine structures in the molecule was added and mixed in an amount of 4 parts by weight based on 100 parts by weight of the solid content of the varnish. Except for the above, a prepreg having a total resin content of 50% was obtained in the same manner as in the method of Example 1 above.

After the prepregs obtained in the above Examples 1 to 8 and Comparative Examples 1 to 3 were prepared and stored in an atmosphere of 20 ° C. and 40% RH for 1 week, 8 sheets each of which had a thickness of 1 side. Overlay with 35μm copper foil, sandwich this with 10 cushions each on top and bottom, 1 stainless steel plate,
Heat pressing was performed by pressing one sheet at 80 kg / cm ² . In addition, about Examples 1-8 and the comparative example 1, it heated by the temperature rising curve shown by 2 of FIG. 1, and about the comparative examples 2 and 3, it heated by the temperature rising curve shown by 1 and 2 of FIG. A 1.6 mm phenolic resin laminate was obtained.

Table 1 below shows various characteristics of the phenol resin laminates obtained by heating and press-molding the prepregs obtained in Examples and Comparative Examples, and the evaluation results of the impregnating ability of the varnish into the laminate base material. Show. Further, as an evaluation of the storage stability of the varnish at room temperature, the varnishes of the above Examples and Comparative Examples before prepreg formation were left to stand in an atmosphere of 30 ° C. 40% RH for 3 weeks, and immediately after and 3 weeks later at 150 ° C. The gel time of each was compared.
The results are shown in Table 1.

[0030]

[Table 1]

In Comparative Example 1, since the amount of the compound having a plurality of amine structures added in the molecule was too large, resinification at room temperature proceeded, impregnation into the laminated base material deteriorated, and the prepreg was stored. The resinification reaction proceeded inside and the fluidity of the resin disappeared, and a normal plate was not obtained. In Comparative Example 2, since the compound having a plurality of amine structures in the molecule was not added, the crosslink density did not increase and the punching workability was poor even when the heating and pressing time was extended. In Comparative Example 3, when diaminodiphenylmethane having only a primary amine was added instead of the compound having a plurality of amine structures in the molecule, the temperature rising curve was 1 in FIG. The curve was defective in 2 of FIG.

As is clear from the results of Tables 1 and 2, the phenol resin laminate obtained according to the present invention has excellent storage stability of varnish at room temperature and excellent curability even in a short laminate molding time. It has excellent punching workability, mechanical properties, electrical properties, and water resistance, and can be suitably used for printed wiring boards.

[Brief description of drawings]

FIG. 1 shows a heating and heating curve of a method for manufacturing a laminated board in an example of the present invention.

Claims (8)

[Claims] 1. A composition comprising 100 parts by weight of a phenol-formaldehyde resin containing 60 to 90% by weight of a drying oil modified phenol-formaldehyde resin and 0.1 to 20 parts by weight of a compound having a plurality of amine structures in the molecule. A resin composition for laminated boards, which is characterized. 2. A laminated sheet, which is obtained by impregnating and drying the resin composition for laminated sheet according to claim 1 on a fibrous sheet-shaped substrate, laminating, and then heat-pressing to integrally mold. 3. The resin composition for laminates according to claim 1, wherein the compound having an amine structure of claim 1 is a compound having only a plurality of secondary amines in the molecule. 4. The resin composition for a laminate according to claim 1, wherein the compound having an amine structure of claim 1 is a compound having only a plurality of tertiary amines in the molecule. 5. The resin composition for a laminate according to claim 1, wherein the compound having an amine structure of claim 1 is a compound having a primary amine and a secondary amine in the molecule. 6. The resin composition for a laminate according to claim 1, wherein the compound having an amine structure of claim 1 is a compound having a primary amine and a tertiary amine in the molecule. 7. The resin composition for a laminate according to claim 1, wherein the compound having an amine structure of claim 1 is a compound having a secondary amine and a tertiary amine in the molecule. 8. The resin composition for a laminate according to claim 1, wherein the compound having an amine structure according to claim 1 is a compound having a primary amine, a secondary amine and a tertiary amine in the molecule.