JPH0892462A - Resin composition for laminate and laminate produced using the same - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. for a quick-curing phenol resin laminate excellent in stability around room temp. and in curability at high temp. by compounding a specific phenol-formaldehyde resin with a specific compd. CONSTITUTION: This resin compsn. comprises 100 pts.wt. phenol-formaldehyde resin contg. 60-90wt.% drying-oil-modified phenol-formaldehyde resin and 0.1-20 pts.wt. metal salt of an inorg. or org. acid. Fibrous sheet substrates are impregnated with the compsn., dried, stacked, and integrally molded under heating and pressure, thus giving a laminate. The drying-oil-modified phenol- formaldehyde resin is obtd. by reacting a drying oil with a phenol compd. in the presence of an acid catalyst and reacting the resultant product with formaldehyde in the presence of a base catalyst to form a resole. Examples of the inorg. acid are hydrochloric, sulfuric, nitric, and phosphoric acids, and examples of the org. acid are acetic, oxalic, malonic, maleic, and sulfonic acids.

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 added to 0.1 part of an inorganic acid or organic acid salt of a metal element. ~ 2
It is a resin composition for a laminated board to which 0 part by weight is added, and is a phenol resin laminated board having the above-mentioned excellent properties obtained by impregnating and drying this on a substrate for a laminated board, laminating, laminating and molding. .

The metal elements used in the present invention include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, titanium, vanadium, chromium, manganese, iron, cobalt and nickel.
Zirconium, transition metals such as platinum, other copper, zinc,
Examples include silver, bell, lead, bismuth, and the like. Inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, and organic acids include acetic acid, oxalic acid, malonic acid, maleic acid, sulfonic acid and the like, and one or more of these salts are used in combination. It is necessary.

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 plate of the present invention is prepared by dissolving an inorganic acid or organic acid of a metal element in a solvent, and then adding it to a dry oil-modified phenol / formaldehyde resin to dissolve it into a varnish, impregnating it on a base material such as kraft paper and drying it. Usually, it can be obtained by laminating 3 to 10 sheets and heat-pressing.

The amount of the inorganic acid or organic acid of the metal element added to the phenol / formaldehyde resin is preferably 0.1 to 20 parts by weight, more preferably 1 part by weight with respect to 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 is extremely shortened, 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.

[0012]

The phenol resin laminate obtained in the present invention has a crosslinking rate (particularly the crosslinking rate of the drying oil-modified resole) due to the catalytic action of the metal element contained in the resin component for varnish at a high temperature by the inorganic or organic acid. It is considered that the curability is excellent and the punching workability, mechanical properties, electrical properties, and water resistance are good because the crosslink density increases and a sufficient crosslink density can be obtained even in a short molding time.

[0013]

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 was chlorinated as an inorganic acid of a metal element. The varnish obtained by adding and mixing 7 parts by weight of cobalt was impregnated into kraft paper and dried to obtain a total resin content of 5
0% prepreg was obtained.

(Example 2) The same procedure as in Example 1 was repeated except that nickel chloride was added and mixed as an inorganic acid of a metal element to 4 parts by weight of varnish solid content of 100 parts by weight. A prepreg having a resin content of 50% was obtained.

(Example 3) The same procedure as in Example 1 was repeated except that 5 parts by weight of iron (II) sulfate as an inorganic acid of a metal element was added and mixed with 100 parts by weight of the solid content of varnish. As a result, a prepreg having a total resin content of 50% was obtained.

(Example 4) The same procedure as in Example 1 was repeated except that copper (II) sulfate was added as an inorganic acid of a metallic element to 8 parts by weight of 100 parts by weight of varnish solid content and mixed. As a result, a prepreg having a total resin content of 50% was obtained.

Example 5 As an organic acid of a metal element, sodium acetate was added to 3 parts by weight of varnish solid content of 3 parts by weight.
A prepreg having a total resin content of 50% was obtained in the same manner as in the above-mentioned Example 1 except that the addition and mixing of parts by weight were added.

Example 6 The same procedure as in Example 1 was repeated except that 7 parts by weight of zinc acetate was added as an organic acid of a metal element to 100 parts by weight of varnish solid content and mixed. A prepreg having a resin content of 50% was obtained.

(Example 7) As an organic acid of a metal element, the same procedure as in Example 1 was repeated except that 9 parts by weight of cobalt acetate was added to 100 parts by weight of varnish solid content and mixed. A prepreg having a resin content of 50% was obtained.

Example 8 As an organic acid of a metal element, dipotassium oxalate was added to 3 parts by weight of a varnish solid content of 3 parts by weight.
A prepreg having a total resin content of 50% was obtained in the same manner as in the above-mentioned Example 1 except that the addition and mixing of parts by weight were added.

Example 9 The same procedure as in Example 1 was repeated except that 5 parts by weight of disodium maleate as an organic acid of a metal element was added and mixed with 100 parts by weight of the solid content of varnish. A prepreg having a total resin content of 50% was obtained.

Example 10 As an organic acid of a metal element,
Zinc acetate was added to 0.7 per 100 parts by weight of solid content of varnish.
A prepreg having a total resin content of 50% was obtained in the same manner as in the above-mentioned Example 1 except that the addition and mixing of parts by weight were added.

(Example 11) As an organic acid of a metal element,
A prepreg having a total resin content of 50% was obtained in the same manner as in Example 1 except that 14 parts by weight of zinc acetate was added and mixed with 100 parts by weight of the varnish solid content.

(Comparative Example 1) As an organic acid of a metal element, zinc acetate was added in an amount of 21 parts by weight to 100 parts by weight of a varnish solid content and mixed, and the same procedure as in Example 1 was repeated. A prepreg having a resin content of 50% was obtained.

(Comparative Example 2) A prepreg having a total resin content of 50% was obtained in the same manner as in Example 1 except that an inorganic acid or an organic acid of a metal element was not added and mixed.

Comparative Example 3 The method of Example 1 except that 4 parts by weight of diaminodiphenylmethane, an amine, was added and mixed with 100 parts by weight of the solid content of the varnish instead of the inorganic or organic acid of the metal element. A prepreg having a total resin content of 50% was obtained in the same manner as in.

After preparing the prepregs obtained in Examples 1 to 11 and Comparative Examples 1 to 3 and storing them in an atmosphere of 20 ° C. and 40% RH for 1 week, 8 sheets of each were prepared.
A copper foil having a thickness of 35 μm was overlaid on one side, and the upper and lower cushions were sandwiched between 10 cushions and 1 stainless steel plate, respectively, and one was pressed at 80 kg / cm ² for heat and pressure molding. 1 to 11 and Comparative Example 1.
No. 2 and the comparative example 2 and 3 were heated by the temperature rise curves shown in 1 and 2 of FIG.
To obtain a phenol resin laminated plate.

Table 1 and Table 1 below show various properties of the phenolic resin laminates obtained by heat-pressing the prepregs obtained in Examples and Comparative Examples and the evaluation results of the impregnating ability of the varnish into the laminate base material. It shows in Table 2. 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 Tables 1 and 2.

[0032]

[Table 1]

[0033]

[Table 2]

In Comparative Example 1, since the amount of the inorganic acid or organic acid of the metal element added was too large, the resinization at room temperature proceeded to impair the impregnation into the laminated base material, and during storage of the prepreg. The resinification reaction proceeded and the fluidity of the resin disappeared, and a normal plate was not obtained. In Comparative Example 2, since the inorganic acid or organic acid of the metal element was not added, the crosslink density did not increase and the punching workability became poor even when the heating and pressing time was lengthened. In Comparative Example 3, when diaminediphenylmethane, which is an amine, was added instead of the inorganic acid or the organic acid of the metal element, the punching workability was good in 1 of FIG. 1, but the heating curve was 2 in FIG. It became defective.

[0035]

As is clear from the results of Tables 1 and 2, the phenolic resin laminate obtained according to the present invention has excellent storage stability of varnish at room temperature and excellent curability even in a short lamination 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.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display area C08J 5/24 CFA C08K 3/24 5/098

Claims (2)

[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 an inorganic acid or organic acid salt of a metal element. A resin composition for a laminated board. 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.