JPH01229043A - Production of phenolic resin laminate - Google Patents

Abstract

PURPOSE:To obtain the title resistance having excellent flame retardance and punchability by blending phenolic resin varnish with a compound obtained by reacting a diglycidyl ether such as a halogen-substituted bisphenol with a polybutadienedicarboxylic acid as a flame-retardant. CONSTITUTION:(A) Hydrogen of phenolic hydroxyl group of (i) a halogen- substituted bisphenol (e. g., tetrabromobisphenol A) or (ii) a halogen-substituted 1,4-dihydroxybenzene, etc., is replaced with glycidyl group to give a compound shown by formula I [ is halogen; Y is group shown by formula II (k and j are 0-4); l and m are 0-4] or formula III (X is halogen; n is 1A 4). 1mol of the compound is reacted with (B)0.1-1mol alpha,omega-polybutadienedicarboxylic acid shown by formula IV (Z is group shown by formula V;Q is group shown by formula VI; t and p are >=0 and t+p>=1) to give a flame-retardant. Phenolic resin varnish is blended with the flame-retardant to give the aimed laminate.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a phenolic resin laminate.

[Prior Art] Recently, there has been a demand for flame retardancy for cellulose-based phenolic resin laminates, which are used as insulating materials for electrical and electronic components, from the viewpoint of safety, and for dimensional accuracy. It is desired to improve punching workability from the viewpoint of improvement and reduction of processing costs. Until now, regarding flame retardation of phenolic resins, there have been methods using halogen compounds, as shown in JP-A No. 60-192732, etc., and methods using halogen compounds, as shown in JP-A No. 5B-8749, etc. There is a method of using a halogen compound and a phosphorus compound together. In order to improve the punching processability, there are methods such as modifying the phenolic resin with vegetable oil or the like and using various plasticizers.

[Problem to be solved by the invention]

However, when using additive flame retardants that do not react with phenolic resins, such as halogen compounds and phosphorus compounds, there is a problem that the heat resistance and solvent resistance of the resin are poor; If a halogenated epoxy resin or the like is used, the storage stability of the varnish will be poor, and if this varnish is used for a laminate, the punching processability of the laminate and the storage stability of the prepreg will be affected. The problem was that it was inferior.

Further, when the amount of modification of vegetable oil or the like or the amount of plasticizer is further increased in order to improve the punching processability, there is a problem that flame retardancy decreases and heat resistance and solvent resistance are inferior.

The present invention has been made based on the above circumstances, and its purpose is to provide a method for manufacturing a phenolic resin laminate having excellent flame retardancy and punching workability.

[Means for Solving the Problems] The method for producing a phenolic resin laminate of the present invention is based on the general formula (I
a) [However, in the formula, X represents a halogen atom, and Y represents CK
Hz to ◆1 ~C- C, H, j◆1 (where k and j each represent an integer of 0 to 4, C0 represents hydrogen, and +j≧1), h (however, W is 0 represents an integer of ~10), l and m
each represents an integer from 0 to 4, Xo represents hydrogen, and 1+m≧1. Note that X may be of the same type or different types. ] Or general formula (Ib) OX, O [However, in the formula, per mole of one or more compounds represented by formula (II) HOOC-(Z)t-(Q)F-COOH(I[) [
However, in the formula, Z represents the following repeating unit -CHz-CH=C)l-C1lt-, and Q represents the following repeating unit -C)1. -CH- C41=CH1, L and p represent integers of 0 or more, and t+P≧
1, and the arrangement of Z and Q is random, and may be alternate or block. A base material is impregnated with a phenolic resin varnish containing a flame retardant compound obtained by a reaction under heating, and then dried to form a prepreg, which is then laminated in multiple layers, and copper foil is placed on top of it. It is characterized by heat forming without overlapping or overlapping copper foil.

Note that the laminate herein refers to both a copper-clad laminate and a laminate that does not use copper foil.

Examples of the halogen atom X in general formulas (Ia) and (Ib) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a bromine atom is particularly preferred.

Among the compounds of the general formula (Ia), 1 and m in the cough formula are l + m = 2 to 4, especially l = m = 1 or l
=m=2 can be suitably used.

Among the compounds represented by the general formula (I a), examples of compounds that can be normally used suitably include the following phenol water metal compounds of bisphenols in which the benzene nucleus is substituted with a halogen atom. can be mentioned. That is, the halogen-substituted bisphenols include tetra such as tetrabromobisphenol A, tetrahalobisphenol AF such as halobisphenol A1 tetrabromobisphenol AF, tetrahalobisphenol B such as tetrabromobisphenol B, tetrabromobisphenol E such as tetrabromobisphenol E, etc. Tetrahalobisphenol F such as halobisphenol E and tetrabromobisphenol F1 Tetrahalobisphenol S such as tetrabromobisphenol S1 Dihalobisphenol A such as dibromobisphenol A1 Dihalobisphenol such as dibromobisphenol AF, dibromobisphenol B, etc. Dihalobisphenol E such as dihalobisphenol B1 and dibromobisphenol E
, dihalobisphenol F such as dibromobisphenol F, and dihalobisphenol S such as dibromobisphenol S. Among these, bromo-substituted products are preferred, and tetrabromobisphenol A and the like are particularly preferred.

Among the compounds represented by the general formula (Ib), specific examples of those usually suitably used include the following phenolic hydroxides of halogen-substituted 1,4-dihydroxybenzenes. can be mentioned. That is, the halogen-substituted 1,4-dihydroxybenzenes include, for example, 2,5-dihalo-1,4-dihydroxybenzene such as 2,5-dibromo-1,4-dihydroxybenzene, 2,3,5. 6-tetrapromo 1
．． Examples include 2.3°5.6-tetrahalo1,4-dihydroxybenzene such as 4-dihydroxybenzene, and among these, bromo-substituted products are particularly preferred.

Among the compounds exemplified above, particularly preferred ones include, for example, diglycidyl ether to tetrabromobisphenol.

As the component, one type of compound selected from the compound represented by the general formula (Ia) and the compound represented by the general formula (Ib) may be used alone, or two or more types of compounds may be used. May be used together.

As the α,ω-polybutadiene dicarboxylic acid represented by the general formula (II), those having a number average molecular weight of about 300 to 2000 can be suitably used. If the number average molecular weight is less than 300, the resulting resin may not have a sufficient flexibility effect when used in resins such as phenolic resins, while if it is greater than 2000, the viscosity will be low. It may become expensive and difficult to use. In addition, the ratio of repeating units Z and Q in general formula (It), that is, the ratio of t and p, is not particularly limited, but is usually t:P=5.
-100:95-0 can be suitably used.

If this ratio of t is too small, a sufficient flexibility effect may not be obtained. Generally, the greater the proportion of t, the greater the flexibility effect, while the greater the proportion of p, the greater the intermolecular reactivity due to the vinyl groups on the side necks.

A reaction mixture of 0.1 to 1 mole of component (■) per mole of component (I a) or (Ib) is added to the phenol resin as a flame retardant. The ratio of the components in (■) can be arbitrary as long as the desired properties are obtained, but it is 0.
．． If the amount is less than 1 mol, the storage stability of varnishes and prepregs will be poor, and when formed into a laminate, the plasticizing effect of the resin will be small, resulting in poor punching workability. Moreover, if the amount of component (n) exceeds 1 mole, the amount of unreacted component (n) increases, which is not preferable.

The blending amount of the flame retardant is preferably 5 to 100 parts by weight per 100 parts by weight of the phenol resin. Further, at this time, other flame retardants such as phosphorus-based, nitrogen-based, and inorganic flame retardants can also be used in combination. The phenol resin is not particularly limited, but a dry vegetable oil-modified resol type phenol resin is preferably used.

A predetermined amount of phenolic resin varnish containing the flame retardant is impregnated onto a cellulose base material, dried to form a prepreg, a predetermined number of sheets of this prepreg are laminated with copper foil as needed, and molded under heat and pressure. A laminate is thereby obtained. The laminate produced by the above method is hard, flame retardant, and has excellent punchability, and can be used as a circuit board for consumer electronic equipment.

(Examples) Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Synthesis of base resin 1 Equipped with stirrer, cooler and thermometer 5! 1,000 g of tung oil, 1,500 g of m, p-cresol, and 1 g of para-toluenesulfonic acid were mixed in a Lasco, and the mixture was reacted at 90°C for 1 hour. Next, 500 g of phenol was added to this reaction solution, followed by 750 g of 80% paraformaldehyde and 70 g of 25% aqueous ammonia, and the mixture was reacted at 80° C. for 4 hours. The condensation water was distilled off, and the end point was the gel time of 3 minutes and 30 seconds on a hot plate at 160°C.
And so.

Synthesis of Base Resin 2 1500 g of tung oil, 1125 g of m, p-cresol, and 1 g of p-toluenesulfonic acid were mixed in a 51 flask equipped with a stirrer, a condenser, and a thermometer, and reacted at 90 °C for 1 hour. To this reaction solution, 375 g of phenol was added, followed by 675 g of 80% paraformaldehyde and 70 g of 25% aqueous ammonia, and the mixture was reacted at 80° C. for 3.5 hours.

The condensation water was distilled off, and the end point was the point at which the reaction product gelled on a hot plate at 160°C for 3 minutes 20 seconds, and the base resin 2
And so.

Synthesis of flame retardant C 550 g of 60% toluene solution of tetrabromobisphenol A diglycidyl ether, 390 g of α-ω-polybutadiene dicarboxylic acid (number average molecular weight 1300.1.2-polybutadiene component 85%), tetramethylammonium chloride 0 0.5 g was introduced into 22 40 flasks and reacted at 110°C for 3 hours, and then used as flame retardant C.

Example 300g of flame retardant C was added to 800g of base resin 1 (resin solid content 70% by weight) synthesized with the above formulation, and varnish A was prepared.
And so.

Comparative Example 1 Varnish B was prepared by adding 200 g of tetrabromobisphenol A diglycidyl ether as a flame retardant to 800 g of Base Resin 1 synthesized with the above formulation.

Comparative Example 2 Varnish C was prepared by adding 150 g of tetrabromobisphenol A diglycidyl ether and 75 g of liphenyl phosphate as flame retardants to 800 g of base resin 1 synthesized with the above formulation.

Comparative Example 3 Varnish D was prepared by adding 285 g of tetrabromobisphenol A diglycidyl ether to 800 g of base resin 2 (resin solid content: 67% by weight) synthesized with the above formulation.

15% each of antimony trioxide sb and o as flame retardant additives were added to the varnishes prepared in the above examples and comparative examples 1.2.3.
g was added, and a mixed solvent of toluene-methanol (1:1) was further added so that the resin content of the system was 60% by weight. Next, a cotton linter was impregnated with these varnishes so that the adhesion resin content was 55% by weight, and dried to produce a prepreg. A predetermined number of sheets of the prepreg were stacked and heated at 170°C under a pressure of 120 kg/crA.
Heat molding was performed for 00 minutes to obtain a laminate. The laminate is JIS-
The characteristics were measured according to the measurement method described in C-6481 and UL-94.

The results are shown in Table 1.

As is clear from the results in Table 1, the phenolic resin laminate of the present invention has excellent flame retardancy and punching workability without degrading various properties of the resin. Comparative example 2
．． In the conventional method for improving punching workability shown in No. 3, the solvent resistance or heat resistance deteriorates significantly.

(Effects of the Invention) The phenolic resin laminate of the present invention has excellent flame retardancy and punching workability without deteriorating the various properties of the resin, and its industrial value is extremely large. be.

Claims (1)

[Claims] 1. General formula (Ia) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(Ia) [However, in the formula, X represents a halogen atom, and Y represents ▲mathematical formula,
There are chemical formulas, tables, etc.▼ (Here, k and j each represent an integer from 0 to 4, and C_
0 represents hydrogen and k+j≧1), ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2-, -
S-, -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, w is 0 to 1
represents an integer of 0), l and m each represent an integer of 0 to 4, , X_0 represents hydrogen, and l+m≧1. Note that X may be of the same type or different types. ] Or general formula (I b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I b) [However, in the formula, X represents a halogen atom, and n represents an integer from 1 to 4. Note that X may be of the same type or of different types. ] General formula (II) HOOC-(Z)_t-(O)_p-COOH(II) [
However, in the formula, Z represents the next repeating unit -CH_2-CH=CH-CH_2-, Q represents the next repeating unit ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and t and p are integers of 0 or more. represents, and t+p≧
1, and the arrangement of Z and Q is random, and may be alternate or block.] α,ω-Polybutadiene dicarboxylic acid 0.1
A base material is impregnated with a phenolic resin varnish containing a flame retardant compound obtained by heat-reacting ~1 mole in the presence of a catalyst, and then dried to form a prepreg, which is then laminated in multiple layers. A method for producing a phenolic resin laminate, which is characterized by heating and forming the phenolic resin laminate with a steel foil layered thereon or without a copper foil layered thereon. 2. The method for producing a phenolic resin laminate according to claim 1, wherein the phenolic resin is a resol type phenolic resin modified with dry vegetable oil. 3. The method for producing a phenolic resin laminate according to claim 1 or 2, wherein the compound used as component (Ia) is diglycidyl ether of tetrabromobisphenol A. 4. The number average molecular weight of the compound represented by general formula (II) is
within the range of 300 to 2000, and repeating unit Z
The method for producing a phenolic resin laminate according to claim 1, claim 2, or claim 3, wherein the ratio of t:p = 5 to 100:95 to 0.