JPS6069149A - Crosslinkable vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a crosslinkable vinyl chloride resin compsn. which gives moldings having excellent mechanical characteristics and is suitable for use in the production of building materials, by mixing a vinyl chloride resin, crystalline calcium silicate and a dithiol-S-triazine compd. CONSTITUTION:5-200pts.wt. crystalline calcium silicate such as xonotlite, tobermorite or wollastonite and 0.2-10pts.wt. dithiol-S-triazine compd. (metal salt) of the formula (wherein R is OR<1>, SR<2>, NR<3>R<4>, phenyl, naphtyl, etc.; R<1>, R<2>, R<3>, R<4> are each H, a monovalent hydrocarbon group) such as 2-dibutylamino-4,6- dithiol-S-triazine are blended with 100pts.wt. vinyl chloride resin such as vinyl chloride resin or a vinyl chloride/vinyl acetate copolymer to obtain the desired crosslinkable vinyl chloride resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinkable vinyl chloride resin composition, and particularly to a crosslinkable vinyl chloride resin composition that provides a molded article with mechanical properties sufficient for practical use as a building material. The purpose is to provide a resin composition.

Conventionally, polyvinyl chloride resin molded products have been used in a wide range of fields such as construction materials due to their well-balanced mechanical properties and price, and hard molded products include pipes, corrugated sheets, decking materials, window frame materials, etc. In addition, various soft molded products such as flooring materials, wire covering materials, films, and sheets are manufactured.

However, there are two types of vinyl chloride resin molded products.

Various attempts have been made to further improve heat resistance or mechanical strength, and one of the modification methods is to crosslink vinyl chloride resin.

Specifically, to vinyl chloride resin, ■ a radical generator such as peroxide, ■ a crosslinking aid having peroxide and a polyfunctional group, or ■ a nuclear crosslinking agent such as diamine or tetramine are added. The composition or (2) a vinyl chloride resin composition into which a group that is easily crosslinked is crosslinked by radiation or thermally (crosslinked by heating 52). However, radiation crosslinking requires large-scale irradiation equipment, is expensive, and is not a common method because it is limited in terms of use. In addition, the method of thermally crosslinking the above composition has problems such as promoting the discoloration and decomposition of the vinyl chloride resin at the same time as crosslinking, significantly impairing the appearance, and causing scorch in the molding machine, making it impossible to mold. There is.

On the other hand, it is also known that the heat resistance and dimensional stability of molded products can be improved by adding a large amount of reinforcing inorganic fillers to vinyl chloride resins. However, in order to improve heat resistance and dimensional stability, it is necessary to add a very large amount of these fillers, and this addition of a large amount may adversely affect the machine of the molded product. There is a problem in that when the mechanical strength is lowered, the side workability of molding is significantly inhibited.

The present invention solves these conventional problems and provides a vinyl chloride resin composition that can produce molded products with sufficient mechanical properties that can be put to practical use as building materials, etc. is a vinyl chloride resin to which crystalline calcium silicate and a dithiol-8-) riazine compound are added.

According to the present invention, the above-mentioned problems caused by the discoloration of the vinyl chloride resin during thermal crosslinking or the high filling of the reinforcing inorganic filler are solved, and the physical properties originally possessed by the vinyl chloride resin are impaired. Thermal crosslinking can be uniformly carried out without any oxidation, and impact resistance, rigidity, one-dimensional stability, flame resistance, etc. can be significantly improved.

The present invention will be explained step by step below.

The vinyl chloride resin used in the present invention is not limited to vinyl chloride homopolymers, but includes copolymers and graft copolymers mainly composed of vinyl chloride.

Furthermore, G2 includes a poly blend mainly composed of vinyl chloride resin. Comonomers copolymerized with vinyl chloride include vinyl acetate, vinylidene chloride, acrylic acid and its esters, acrylonitriles, ethylene,
Examples include olefins such as propylene, maleic acid and its anhydride, and these may be used alone or as a mixture of two or more. In addition, resins to be blended with vinyl chloride resin include ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer. Examples include styrene copolymers, chlorinated polyethylene, and nitrile-butadiene copolymers.

The present invention relates to the above-mentioned vinyl chloride resin.

Crystalline calcium silicate and dithiol-S-triazine compound are blended, and this crystalline calcium silicate is generally a synthetic calcium silicate obtained by hydration reaction of lime and silicic acid. (Sheet trial in which crystals were generated by applying controlled temperature and pressure) (60aO・The amount of the above crystalline calcium silicate is 5 to 200 parts by weight per 100 parts by weight of vinyl chloride resin)
Parts by weight preferably range from 10 to 100 parts by weight.

Next, the dithiol-8-triazine compound used in the present invention has the general formula (wherein R is a group represented by OR", SR", NR"R', a phenyl group, a naphthyl group, a morpholyl group, , where R'', R'', R'' and R4 are each 1
; a hydrogen atom or a monovalent hydrocarbon group) and metal salts thereof. Among these, the crosslinking effect of vinyl chloride resins is that R is large in basicity, such as NR'' R4, SFF.

OR". As such dithiol-8-) riazine compounds, R is a 2-dimethylamino group, 2-dibutylamino group, 2-octylamino group, 2-cyclohexylamino group, 2 -benzylamino group, 2-dibenzylamino group.

2-phenylamino group, 2-phenylbenzylamino group, 2-methylphenylamino group, 2-anilino group, 2-
Diphenylamino group, 2-α-naphthylamino group, 2-
Examples include compounds such as a β-naphthylamino group, a 2-pentylthio group, a 2-ethoxy group, and a 2-phenoxy group. Examples of the metal salt of the dithiol-8-)riazine compound include alkali metal salts, alkaline earth metal salts, and other metal salts such as A1.8n, Pb, and Ni.

The amount of the dithiol-8-)riazine compound or its metal salt to be blended is preferably in the range of 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. .

It is already known that the above-mentioned dithiol-8-) riazine compound exhibits a crosslinking effect on vinyl chloride resin. In this case, the crosslinking reaction progresses due to shear heat generation during molding, making it difficult to control the crosslinking reaction, which accelerates thermal decomposition of the vinyl chloride resin, making it difficult to obtain molded products for practical use.

However, the second surprising thing is dithiol-8.
-) By using a riazine compound and crystalline calcium silicate in combination, the crosslinking reaction of the vinyl chloride resin progresses favorably, and during this thermal crosslinking reaction (no decomposition of the vinyl dichloride resin occurs). The molded product obtained from the crosslinkable vinyl chloride resin composition of the present invention has the following characteristics: C: does not soften or flow during combustion, and burns and carbonizes while retaining its original shape. It has the effect of capturing hydrochloric acid gas generated during combustion.

In addition, in the present invention, a reactive plasticizer having at least two polymerizable unsaturated bonds, which is commonly used for crosslinking of vinyl chloride resin, is used in combination, and other general plasticizers and fillers are also used. , stabilizer.

It is free to add lubricants, ultraviolet absorbers, pigments, etc.

To advance the crosslinking reaction, a normal thermal crosslinking method is generally used, but active energy rays such as alpha rays, beta rays, r rays, ultraviolet rays, and high frequency waves may also be used.

The crosslinkable fecal matter molded product obtained according to the present invention has excellent heat resistance, dimensional stability, rigidity, and flame resistance, and is therefore suitable for use as a building material or a structural member. Application C: Optimal for window frame materials, decorative materials, side wall boards, etc.

In addition, for soft molded products, it is suitable for applications such as long tiles and heat-resistant sheets.

Next, C2 concrete examples will be given.

Examples (Experiments 11 to 5) Five types of compounds shown in Table 1 were prepared.

'#g 1 Table (Blend 0 parts by weight) TK-1000: Shin-Etsu Chemical Co., Ltd., vinyl chloride resin, average degree of polymerization 1050 PE-520: Hoechst Co., Ltd., polyethylene wax 0P-Wax: Hoechst Co., Ltd., Ester Wax TM
-181FB, T: Manufactured by Katsuyama Kako ■, methyl tin mercaptide stabilizer Product properties Calcium silicate A blend of the above composition was rolled in a 6-inch roll at 185°C for 5 minutes.
After kneading for a minute to make a roll sheet, stack it up and
Pressure molding was performed at 90° C. and a pressure of 60 KP/cd to obtain a press molded product with a thickness of 1”.

A physical property test was conducted at 20° C. in accordance with JIS K6745 C, and the appearance (N color) and degree of crosslinking of the pressed plate were measured by THF insoluble content measurement, and the following results were obtained.

Table 2 = Vinyl chloride resin compositions using a β-triazid V compound in combination, when the crosslinking agent was used alone (Experiment 3), when the inorganic secondary acid calcium was used (Experiment 4), When using calcium silicate alone (Experiment 1'11IX5
), there is no coloring and decomposition of the resin, and the crosslinking efficiency is high (rigidity, heat resistance 1: excellent).

Claims (1)

[Scope of Claims] 1. A crosslinkable vinyl chloride resin composition comprising a vinyl chloride resin, crystalline calcium silicate and a dithiol-8-)riazine compound. 2. A vinyl chloride resin with 100 parts of heavy acid, crystalline silica. The crosslinkable vinyl chloride resin composition 3 according to claim 1, comprising 5 to 200 parts by weight of calcium silicate and 0.2 to 10 parts by weight of a dithiol-8-)riazine compound, wherein the crystalline calcium silicate is The crosslinkable vinyl chloride resin composition 4 according to claim 1, which is Sheetdryde, tobermorite or wollastonite, wherein the dithiol-8-)riazine compound has the general formula (wherein R is OR"), a group represented by SR'', NR''R', or a phenyl group, a naphthyl group, a morpholyl group, where R1, R1, ul and R4 are each a hydrogen atom or a monovalent hydrocarbon group) The crosslinkable vinyl chloride resin composition according to claim 1, which is a compound and a metal salt thereof.