JPH0393849A - Flame-retardant phenol resin composition - Google Patents

Abstract

PURPOSE:To obtain the title flame-retardant composition having excellent heat resistance providing resin laminate comprising components blended good in compatibility, having excellent electric characteristics and punchability by blending a phenol resin with a specific compound. CONSTITUTION:A phenol resin is blended with a compound shown by the formula (R1 is CH2, C2H4, C3H6, C4H8, C5H10 or C6H12; R2 is H, CH3, C2H5, C3H7, C4H9 or C5H11; X is Cl or Br; n is 1-4 and m is 1-5). The amount of the phenol resin is 3-50wt% based on the phenol resin. An adduct of dibromoisopropylphenol, dibromocresol, tribromophenol or tribromocresol with an alkylene oxide may be cited as the compound.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a flame-retardant phenolic resin assembly with excellent heat resistance and excellent electrical properties and good punching workability for use in resin laminates, etc. It is related to precepts. [Prior Art] Recently, insulating materials, especially laminates used for communication equipment and electronic equipment, have been developed to have excellent punching properties at room temperature or relatively low temperatures near room temperature, from the viewpoint of automation of processing equipment and energy saving. Something is demanded. Therefore, phenolic resins modified with drying oil, etc., are usually used as resins for laminates, using various alkylphenols in combination with phenol. On the other hand, there is a growing demand for flame retardancy for laminates used as insulating materials due to increased emphasis on safety. Conventionally, laminates are made flame retardant in two ways: additive flame retardants, in which halogen or phosphorus compounds are added to the resin, and reactive flame retardants, which are chemically bonded to the resin. Each has advantages and disadvantages. When using reactive flame retardants, if they are used in large quantities, flexibility decreases and punching workability at constant temperature decreases. On the other hand, when additive flame retardants are used, the flame retardant remains unreacted in the product, resulting in a decrease in heat resistance. [Problems to be Solved by the Invention] The present invention relates to a flame-retardant phenolic resin composition that provides a resin laminate with excellent heat resistance without deteriorating electrical properties or other properties. [Means for solving the problem] l. The present invention provides phenolic resin with (R+: CH*, CxHa, C.H., C 4 H
s. C s H +. , ChHI! % Ri:H, CHs, CtHs, C. H,,C*H
w. CsH++, X: Cl, Br, n- 1-4
, m-1 to m-5) to provide a flame-retardant phenolic resin composite having the various excellent properties described above. The phenol resin used in the flame-retardant phenol resin composition of the present invention is a product made by reacting phenols with formaldehyde such as paraform and formalin aqueous solution, and examples of the phenols include phenol, cresol, propylphenol, butylphenol, nonylphenol,
C, ~CtO alkylphenol such as cashew dimer. The reaction between phenols and formaldehyde uses acidic and basic catalysts. Acidic catalysts include oxalic acid, sulfuric acid, para-toluenesulfonic acid, etc., and novolac type phenolic resins are obtained. Further, as basic catalysts, hydroxides such as sodium hydroxide and aqueous ammonia, etc., can be used to obtain resol type phenolic resins. In the present invention, any of them can be used. It is also possible to use oil-modified phenolic resins modified with oils such as tung oil, linseed oil, dehydrated mustard oil, and cashew nut oil as the phenolic resin. Examples of the compound (I) include dipromisopropylphenol, dipromcresol, tribromphenol, and alkylene oxide adducts of tripromcresol. The amount of compound (I) to be used is not limited to the following range, but it should be set at 3 to 50 parts by weight per 100 parts by weight of the phenol resin fixed material. is preferable. If the amount used is less than 3 parts by weight, the flame retardant tends to be insufficient, and if it exceeds 50 parts by weight, electrical properties etc. tend to deteriorate.

Compound (1) used as a flame retardant in the present invention not only has excellent flame retardancy because it has a halogen bonded to it, but also has an alkyl ether structure and a hydroxyl group at the end, so it has phenol It has excellent compatibility with resins, and even though it is an additive flame retardant, it is uniformly dissolved in the resin even in the cured product, so it rarely reduces the heat resistance of the resin. [Example] The present invention will be explained below with reference to Examples. 850 g of tung oil, 1200 g of metacresol, and 2 g of para-toluenesulfonic acid were mixed and reacted at 90°C for 90 minutes. Next, 100 g of nonylphenol, 100 g of paraform, and 10 g of 25% aqueous ammonia were placed in a reaction vessel and reacted at 85°C for 2 hours. Water was then removed under reduced pressure and a solvent was added to produce a resin varnish. The propylene oxide adduct of tribromophenol (Br content 57%
>10 parts by weight was added. Cotton linter paper was impregnated with the above varnish and dried to produce a resin-impregnated base material with a resin adhesion content of 50 parts by weight. Layer 8 sheets of this base material,
6 under lamination conditions of 160-165”C, 80kg/cd
A phenolic resin laminate with a thickness of 1.6 111 was produced by heat-pressing for 0 minutes. In addition, 10 parts by weight of Ichisaka's flame retardant tetrapromobisphenol A (TBA) was added to the resin solid content of the 1u East L test sheet. A phenolic resin laminate was manufactured in the same manner as in the example below. Comparative Spotting 1 Parts by weight of a commercially available flame retardant, dipromocresol glycidyl ether IQ, were added to the resin solid content of the varnish of the Comparison Example. A phenolic resin laminate was manufactured in the same manner as in the example below. Table 1 shows the various properties of the phenolic resins obtained in Examples and Comparative Examples that are higher than the characteristic values of the first front laminate.

Water absorption, insulation resistance, solvent resistance: JIS C 6481
by. Heat resistance: 230 x 10x10aJ laminate
'C: Heat for 2 minutes to see if blistering occurs. Punching workability: Based on Chochuto 617. As is clear from the above, the flame-retardant phenolic resin composition of the example has properties that satisfy not only flame retardancy but also heat resistance, punching workability, electrical properties, solvent resistance, etc., and the comparative example It is much superior to the conventional I1i flammable phenolic resin shown in 1 and 2.

〔Effect of the invention〕

The flame-retardant phenolic resin & Il material of the present invention is not only flame-retardant, but also has excellent flexibility, electrical properties, and solvent resistance, and can be used for decorative boards, shaped products, laminated products, etc. It is particularly suitable as a resin for laminates, whose required properties are improving year by year. Procedural amendment (voluntary) October 24, 2016

Claims (1)

[Claims] 1. Phenolic resin has ▲mathematical formulas, chemical formulas, tables, etc.▼ (R_1: CH_2, C_2H_4, C_3H_6, C
_4H_8, C_5H_1_8, C_6H_1_2, R_2:H, CH_3, C_2H_5, C_3H_7,
C_4H_9, C_5H_1_1, X: Cl, Br, n
= 1-4, m = 1-5) A flame-retardant phenol resin composition characterized by adding a compound [I]. 2. The amount of compound [I] added is 3 to phenolic resin.
The flame retardant phenolic resin composition according to claim 1, wherein the amount is 50% by weight.