JPH0441546A - Phenol resin composition for laminate, and copper-clad laminate prepared therefrom - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in resistance to tracking, heat, moisture, and chemicals and in punchability by compounding a phenol resin with a melamine resin and a furan resin each in a specified amt. CONSTITUTION:The title compsn. is prepd. by compounding a phenol resin with 5-30wt.% (based on the total compsn.) melamine resin and 3-40wt.% (based on the total compsn.) furan resin. The compsn., excellent in resistance to tracking, heat, and chemicals and in punching, gives a copper-clad laminate giving a circuit board with a high reliability.

Description

[Detailed Description of the Invention] [Purpose of the Invention (Industrial Field of Application) The present invention provides a phenolic resin for lamination with excellent tracking resistance, #4 heat resistance, chemical resistance, punching workability, etc. and related to copper-clad laminates.

(Prior Art) The development of electronic devices in recent years has been remarkable and diversified, and various strict conditions have come to be imposed on the component materials used therein.

Among these, the requirements for substrates are increasing at present.
As a measure against fire accidents in high-voltage applications such as televisions, tracking resistance of 1 is recommended.

In order to improve tracking resistance, polyester resin or melamine-modified phenol resin is used for t.

(Problem to be solved by the invention) However, paper-based laminates using polyester resin,
Although it has excellent tracking resistance, it does not have sufficient moisture resistance and has the disadvantage that it warps when soldered. In addition, although melamine-modified phenolic resin is effective in tracking resistance, it has the disadvantage of being prone to cracking during punching.To solve this problem, adding a large amount of plasticizer reduces the heat resistance of the laminate. However, it had the disadvantage of reduced chemical resistance.

The present invention was made to eliminate the above-mentioned drawbacks, and provides a phenolic resin composition for lamination and a copper-clad laminate that has excellent tracking resistance, heat resistance to moisture resistance, chemical resistance, and punching workability. This is what I am trying to do.

[Structure of the Invention] (Means for Solving the Problems) As a result of extensive research aimed at achieving the above object, the present inventor has found that the above object can be achieved by modifying a phenol resin with a melamine resin and a furan resin. The present invention has been completed based on the discovery that a composition and a copper-clad laminate can be obtained that can achieve the following.

That is, the present invention includes <A) phenol resin, (B) melamine resin, and (C) furan resin as essential components, and the above (B) for the entire resin composition.
This is a phenolic resin composition for lamination, characterized in that it contains 5 to 30% by weight of the melamine resin described above and 3 to 40% by weight of the furan resin (C). Further, the present invention is a copper-clad laminate characterized by using a prepreg obtained by coating and impregnating a paper base material with this phenolic resin composition for lamination.

The (A) phenolic resin used in the present invention is usually
All phenolic resins used for laminates are broadly encompassed and can be used.

Further, the phenolic resin may be modified, and in particular, oil-modified phenolic resin can be preferably used for punching.

These phenolic resins can be used alone or in a mixture of two or more.6 The melamine resin (B) in the present invention is produced by condensing melamine or guanamines such as formguanamine, acetoguanamine, benzoguanamine, and aldehyde to form a methylol group. It refers to a resin containing a methylol group, and includes methylated melamine resins and butylated melamine resins in which the methylol group is etherified with methanol, butanol, etc., and these can be used alone or in a mixture of two or more types. The blending ratio of melamine resin is as solid content:
It is desirable that the content be 5 to 30% by weight based on the total resin composition. If the proportion is less than 5% by weight, it has no effect on tracking resistance, and if it exceeds 30% by weight, the punching workability is unfavorable. Furthermore, a melamine-modified phenol resin modified in the same proportion as the phenol resin and melamine resin can be used instead of the phenol resin and melamine resin.

The furan resin (C) used in the present invention is a resin containing a furan ring, and includes phenol-furfural resin, furfuryl alcohol resin, and the like. Among these, frifuryl alcohol resin can be preferably used to improve tracking resistance.

Specific examples of frifuryl alcohol resins include Hitafuran 302, 303 <manufactured by Hitachi J-Hisei Kogyo Co., Ltd.;
(trade name), etc., and these can be used alone or in a mixture of two or more. It is desirable that the solid content of the furan resin be blended in an amount of 3 to 40% by weight based on the solid content of the entire resin composition. If this proportion is less than 3% by weight, there is no effect on heat resistance and chemical resistance, and if it exceeds 40% by weight, the punching workability at low temperatures is undesirable.

In addition, it is desirable that the total blending ratio of melamine resin and furan resin is 15 to 55% by weight based on the entire resin composition.If this ratio is less than 15% by weight, tracking resistance, heat resistance, No effect on chemical resistance, and 5
If it exceeds 5% by weight, the punching workability will be poor, which is not preferable.

The paper base material and copper foil used in the present invention are not particularly limited, and may be those commonly used for lamination or may be widely used.

The phenolic resin composition for lamination of the present invention contains a phenol resin, a melamine resin, and a furan resin as essential components, or
Flame retardants and other components may be added as long as they do not contradict the purpose of the present invention.

A phenolic resin composition for lamination can be easily produced by blending these components. A prepreg can be made by coating and impregnating a paper base material with this phenolic resin composition for lamination. A copper-clad laminate can be manufactured by stacking a plurality of sheets of this prepreg and copper foil and molding them into an integral body under heat and pressure using a conventional method.

(Function) The phenol core in the phenol resin is easily carbonized, and when carbonized, the tracking and y-king resistance decreases.

On the other hand, although the melamine core of the melamine resin improves tracking resistance, it becomes hard and reduces punching workability. To improve this, a large amount of plasticizer is required, and as a result, the heat resistance and chemical resistance of the laminate deteriorate. For this reason, the present invention introduces furan resin to reduce the proportion of phenol nuclei that are easy to carbonize, thereby fully exhibiting the tracking resistance of melamine nuclei, and also prevents the deterioration of heat resistance and chemical resistance due to the addition of plasticizers. By preventing this by introducing a resin, a phenolic resin composition for a laminate having a good balance of mutual properties including good punching workability was obtained.

(Examples) Next, the present invention will be specifically explained by examples, but the present invention is not limited by the following examples.

[A] Production of phenolic resin Phenol 250 (J,
Prepared 340g of cresol, 300Q of nonylphenol, 350!11 of tung oil and 720q of 37% formalin.
Monomethylamine was added to adjust the pH to 6, and while stirring, the mixture was heated to 100° C. and reacted for 3 hours. Thereafter, it was dehydrated under reduced pressure and diluted with a 7/3 mixed solvent of toluene/methanol, resulting in a resin solid content of 55% by weight and a viscosity of 2.3 poise (
An oil-modified phenol resin solution with a gelation time of 2 minutes and 10 seconds < 150°C) was produced.

[B] Production of melamine resin 310 g of melamine and 3
1200 g of 7% formalin was charged and monoethylamine was added to adjust to 1) H=7, and without stirring, the mixture was heated to 80°C and reacted for 4 hours. After that, the resin was dehydrated under reduced pressure and diluted with methanol, resulting in a resin solid content of 55% by weight and a viscosity of 1.0.1.
-'7s (25°C), gelation time 1 minute 50 seconds (150
Prepare a melamine resin solution at

EXAMPLE A phenol resin composition for a laminate was manufactured by blending a phenol resin, a melamine resin, a furan resin, and other components into the composition shown in Table 1.

Comparative Examples 1 to 2] - W of Comparative Example 12 was mixed according to the composition shown in the table.
A phenolic resin composition for I-layer board was produced.

The phenolic resin compositions for laminates produced in Examples and Comparative Examples 1 and 2 were applied and impregnated onto 10 mils kraft paper to produce prepregs with a resin content of 150% by weight and a microwave flow of 8%. Next, 8 sheets of this prepreg and a thickness of 3
Layer copper foil with 5μ positive adhesive, 170'C, 100kq
A copper-clad laminate having a thickness of 1.6 inches was manufactured by integrally molding the product under heat and pressure for 75 minutes under the conditions of /c12.

This IP-stretched laminate was tested for water absorption, insulation resistance, soldering heat resistance, flame resistance, tracking resistance, punching workability, and chemical resistance. The results are shown in Table 1, and the characteristics of the present invention were excellent, confirming the effects of the present invention.

*1: Manufactured by Hitachi Chemical Co., Ltd., product name.

*2: Bromine-based flame retardant manufactured by Tobu Kasei Co., Ltd., trade name.

*3 Tetrabromodiphenyl ether manufactured by Ni-Daiko Kogyo Seiyaku Co., Ltd., trade name.

*4: Cresyl diphenyl phosphate.

*5: Measured according to JI 5-C-6481.

6: Measured by floating in a solder bath at 260°C.

Ne7: Measured by UL94.

*8: Pattern spacing is 0.5nl, other conditions are ■
Measured according to EC Publication 12.

*9: 1.78nt IC without any defects such as cracks
The surface temperature of the laminate that allows pitch punching.

*10: Evaluate the change in appearance after immersing in 5% sodium hydroxide aqueous solution at 50°C for 30 minutes.

○ mark: No abnormality, × mark: Discoloration.

*11: Evaluated the change in appearance after being immersed in boiling trichlorethylene for 5 minutes.

○ mark: No abnormality, × mark: Discoloration.

[Effects of the Invention] As is clear from the above explanation and Table 1, the phenolic resin composition for laminates of the present invention has tracking resistance,
A highly reliable wiring board can be obtained by using the copper-clad laminate of the present invention, which has excellent heat resistance, chemical resistance, and punching workability, and is well-balanced without impairing other properties. I can do it.

Patent applicant: Toshiba Chemical Corporation Agent Patent attorney 1) Eiji

Claims (1)

[Scope of Claims] 1 (A) phenol resin, (B) melamine resin and (C) furan resin are essential components, and the above (B)
A phenolic resin composition for lamination, comprising 5 to 30% by weight of the melamine resin () and 3 to 40% by weight of the furan resin (C). 2 (A) phenol resin, (B) melamine resin and (C) furan resin are essential components, and the above (B) is added to the entire resin composition.
It is characterized by using a prepreg in which a paper base material is coated and impregnated with a phenolic resin composition for lamination containing 5 to 30% by weight of the melamine resin of (C) and 3 to 40% by weight of the furan resin (C). Copper-clad laminate.