JPH01318046A - Copper-clad phenolic resin laminate - Google Patents

Abstract

PURPOSE:To prepare a copper-clad phenolic resin laminate with excellent fire resistance, heat resistance, punchability and dimensional stability and with less warping, by priming a paper substrate with a specific phenolic resin compsn., then impregnating the substrate with a phenolic resin compsn. used for topcoating to thereby give a prepreg, and laminating the resulting prepreg with copper foils. CONSTITUTION:A phenolic resin compsn. contg., as essential components, phosphoric esters (A) of the formula (m, n are 0, 1-3; m+n is 3), one or more phenols (B) selected from, e.g., (nonyl)phenol, cresol, etc., and formaldehyde (C) and prepd. by the condensation reaction of component A in such a wt. ratio that A/(A+B) is 0.2-0.6 with component C is dissolved in, e.g., an org. solvent, and applied as a primer to a paper substrate in an amount of 2-20wt.% based on the substrate. The paper substrate is then impregnated with a phenolic resin compsn. usually used for topcoating in the form of, e.g., a varnish and dried. The resulting prepreg is laminated with copper foils.

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Field of Application) The present invention provides a phenolic resin that has good flame resistance, moisture resistance, punching workability, dimensional stability, low warping, and a good balance of properties. Regarding copper-clad laminates.

(Prior Art) Melamine resins, water-soluble phenolic resins, and the like have been used as resins for pretreatment of filter paper base materials used in phenolic resin copper-clad laminates.

These pretreatment resins improve the flame resistance or moisture resistance of phenolic resin copper-clad laminates, but on the other hand, they cause warping in the copper-clad laminates and impair punching workability or dimensional stability. It had the disadvantage of lowering the

(Problems to be Solved by the Invention) The present invention has been made to eliminate the above-mentioned drawbacks, and has improved flame resistance, heat resistance, and moisture resistance, as well as less warping, punching workability, and dimensional stability. The present invention aims to provide a phenolic resin copper-clad laminate with excellent properties and well-balanced properties.

[Structure of the Invention] (Means for Solving the Problem) As a result of intensive research aimed at achieving the above object, the present inventors have achieved the following by using the composition described below as a pretreatment resin. The present invention was completed based on the discovery that a phenolic resin #J-clad laminate having excellent flame resistance, heat resistance, moisture resistance, punching workability, and dimensional stability and less warping can be obtained.

That is, the present invention provides: (A) a phosphoric ester represented by the following general formula (wherein and n each represent 0 or an integer of 1 to 3, and Il+n=3); (B) a phenol; and (C) formaldehyde as essential components, and the above (A) phosphoric ester [(
A) + (B)] A first phenolic resin composition prepared by condensation reaction of components blended in an amount of 20 to 60% by weight is applied to a paper base material in an amount of 2 to 20% by weight, and a second A phenolic resin steel-clad laminate characterized by being formed by laminating and molding a prepreg coated with a phenolic resin composition and copper foil, and a first phenol resin composition according to the invention of the above-mentioned phenolic resin copper-clad laminate. It is a phenolic resin composition called.

The phosphoric acid ester (A) used in the present invention is not particularly limited as long as it has the general formula described above. Examples of specific compounds include: The blending ratio of phosphoric acid ester is preferably 20 to 60% by weight based on the entire resin composition.6 If this ratio is less than 20% by weight, sufficient flame resistance cannot be obtained, and If it exceeds 60% by weight, the flame resistance will not improve any further and the electrical properties will deteriorate, which is not preferable.

The phenols (B) used in the present invention include all phenols normally used for laminates, such as phenol, cresol, xylenol, propenylphenol, butylphenol, and nonylphenol.
These may be used alone or in combination of 2a or more.

Examples of the <C> formaldehyde used in the present invention include formalin and formaldehyde, and these can be used alone or in a mixture of two or more.

Examples of the paper base material used in the present invention include linter paper, kraft paper, and mixed paper.

The first phenol resin composition of the present invention is obtained by reacting essential components such as phosphoric acid ester, phenols, and formaldehydes, but the reaction order of each component is not limited and may be in any order.

The phenol resin composition thus obtained is dissolved and diluted in an organic solvent to form a varnish of the first phenol resin composition, and then pretreated as an undercoat on a paper base material such as kraft paper.
Next, a varnish of a second phenolic resin composition commonly used for top coating is impregnated and dried to form a prepreg, and multiple sheets of this prepreg and copper foil are laminated and integrated by heating and pressure lamination molding to form a phenolic resin copper-clad laminate. can be manufactured.

(Function) In the phenolic resin composition of the present invention, the phosphoric acid ester as a flame retardant is reactive with the phenol resin, so it reacts and is incorporated into the molecular core, improving both flame resistance and heat resistance.

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

Example 1 1-60 g of resorcyldiphenylphosphate, 100 g of phenol, 40 g of nonylphenol, 140 g of 37% formalin, and 5 g of triethylamine were added to a four-bottle flask with a condenser, and the mixture was reacted under reflux for 2 hours, and then dehydrated under reduced pressure. By diluting with methanol, a varnish (A) having a resin solid content of 50% by weight, a viscosity of 0.8 poise (25°C), and a gelation time of 4 minutes and 30 seconds (150°C) was produced.

Example 2 Resorcil diphenyl phosphate 40 (1, 130 g of phenol, 30 g of nonylphenol, 140 g of 37% formalin, and 5 g of triethylamine were added to a four-eye flask with a condenser, and the mixture was reacted under reflux for 2 hours. After dehydration under reduced pressure, methanol was added. A varnish (B) having a resin solid content of 50% by weight, a viscosity of 1.0 poise (at 25° C.), and a gelation time of 4 minutes (at 150° C.) was prepared by diluting the mixture.

Comparative Example 1 130g of phenol was placed in a four-loop flask with a condenser.
190 g of 37% formalin and 1 part of triethanolamine
After adding 0g and reacting at 80°C for 2 hours, dehydrating under reduced pressure, diluting with methanol to obtain a resin solid content of 50% by weight.
A varnish <C> having a viscosity of 0.6 Boaz (25° C.) and a gelation time of 3 minutes and 30 seconds (150° C.) was produced.

Comparative Example 2 100g of phenol was placed in a four-loop flask with a condenser.
Nonylphenol 150g, 37% Formylin 1409
and triethylamine 99, reacted under reflux for 2 hours, dehydrated under reduced pressure, and diluted with methanol to obtain a resin with a solid content of 50% by weight and a viscosity of 1.2 poise (25°C).
, varnish with a gelation time of 4 minutes and 30 seconds (150°C) (D)
was manufactured.

Comparative Example 3 Methylol melamine resin Nikalenzi S-260 (manufactured by Nippon Carbide Co., Ltd., trade name) was diluted with methanol, and a varnish (E) with a resin solid content of 50% by weight and a viscosity of 1.2 poise (25'C) was prepared. Manufactured.

200 g of phenol was placed in a four-loaf flask with a capacitor, which is commonly used for the production of top varnish.
Tung oil 1001:l and paratoluenesulfone il O,
After charging 39 and reacting at 100°C for 1 hour, 40
Adjust neutralization with % ammonia water. Next, 250 g of benzoguanamine, 120 q of phenol, 460 g of 31% formalin, and 12 g of dimethylamine were added and reacted under reflux for 2 hours, dehydrated under reduced pressure, diluted with a mixed solvent of toluene:methanol = 1:1, and this Add 341g of triphenyl phosphate to the resin solids content to 55%,
A varnish with a viscosity of 1.8 poise (25"C) and a gel time of 6 minutes and 20 seconds (150C) was produced.

Varnishes (A
) to (E) on 10 mils thick kraft paper.
Next, the above-mentioned top coat varnish was applied and impregnated, and dried to produce a prepreg with a resin adhesion amount of 50% by weight and a range flow of 8%. Eight sheets of this prepreg and a 35 μt thick adhesive-coated copper foil were stacked together and heated at a temperature of 170°C and a pressure of 100 kQ/cn'.
The product was heated and pressure-molded for 5 minutes to produce a phenolic resin single-sided copper-clad laminate having a thickness of 1.6 I. These single-sided copper-clad laminates were tested for water absorption, soldering heat resistance, insulation resistance, flame resistance, and punching workability, and the results are shown in Table 1.

The present invention was excellent in all tests, confirming the remarkable effects of the present invention.

[Effects of the Invention] As is clear from the above explanation and Table 1, the phenolic resin copper-clad laminate of the present invention has improved flame resistance, heat resistance, and moisture resistance, has less warpage, and has excellent punching workability. It is highly reliable with excellent dimensional stability, well-balanced characteristics, and is suitable for consumer electronic devices.

Patent applicant: Toshiba Chemical Corporation ゛q

Claims (1)

[Claims] 1 (A) The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, m and n each represent 0 or an integer from 1 to 3, and m + n = 3. ) The phosphoric ester represented by (B) phenols and (C) formaldehyde are essential components, and the phosphoric ester (A) is [(
The paper base material is undercoated with 2 to 20% by weight of the first phenol resin composition, which is obtained by condensation reaction of components blended at a ratio of 20 to 60% by weight based on A)+(B)], and the second
A phenolic resin copper-clad laminate characterized by being formed by laminating and molding a prepreg coated with a phenolic resin composition and copper foil. 2 (A) Phosphoric acid represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, m and n each represent 0 or an integer from 1 to 3, and m + n = 3) Ester (B) phenols and (C) formaldehyde as essential components, and the above (A) phosphoric ester [(
A phenol resin composition, characterized in that it is formed by condensing components blended at a ratio of 20 to 60% by weight based on A)+(B)].