JPH0236146B2 - ENSOKAENKABINIRUJUSHISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized chlorinated vinyl chloride resin composition, and more particularly to a stabilized chlorinated vinyl chloride resin composition obtained by adding an organotin mercaptide compound and an aluminum compound to a chlorinated vinyl chloride resin. Chlorinated vinyl chloride resin, which is a post-chlorinated vinyl chloride resin, has been developed to improve the heat resistance (softening temperature) of vinyl chloride resin, and its excellent heat resistance, chemical resistance, creep resistance, and It is widely used in various applications due to its properties such as flame retardancy. However, as the chlorine content of chlorinated vinyl chloride resin increases, the softening temperature increases and the heat resistance improves, but at the same time, the disadvantage is that the heat generated by the resin during kneading increases due to the increase in melt viscosity.
Because it approaches its decomposition temperature, it generally has poor thermal stability and is difficult to process. Conventionally, when processing chlorinated vinyl chloride resin, stabilizers used for vinyl chloride resin, such as organotin compounds, metal soaps, and metal inorganic salts, have been used, but their effects are extremely small and are not practically satisfactory. Nakatsuta. Among these stabilizers, organotin mercaptide compounds are relatively effective, but even in this case, they tend to stick to rolls so strongly that it is difficult to continuously obtain sheets. As a result of extensive studies in view of the current situation, the present inventor has found that by adding a specific aluminum compound together with an organotin mercaptide compound, the stability of chlorinated vinyl chloride resin can be significantly increased without deteriorating its physical properties. We have discovered that it is possible to do so and have arrived at the present invention. That is, in the present invention, (a) an organic tin mercaptide compound of 0.01 to 100 parts by weight of a chlorinated vinyl chloride resin is added.
Stabilized chlorination by adding 10 parts by weight and (b) 0.01 to 10 parts by weight of at least one kind of aluminum compound selected from aluminum carboxylates, aluminum organic phosphates, aluminum hydroxide, and hydrotalcites. A vinyl chloride resin composition is provided. The chlorinated vinyl chloride resin used in the present invention can be produced by chlorinating vinyl chloride resin by a well-known method such as a solution method, suspension method, or gas phase method, and has a chlorine content of 60 to 70% by weight. Preferably.
In addition, chlorinated vinyl chloride resin and other resins, such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyethylene, ethylene-vinyl acetate copolymer, ABS resin, AB resin, MBS resin, acrylic resin, etc. It can also be a blend with
In this case, it is preferable that the chlorinated vinyl chloride resin be 40% by weight or more of the total resin. Examples of the organic tin mercaptide compounds used in the present invention include dibutyltin bis(lauryl mercaptide), dimethyltin bis(stearyl mercaptide), dioctyltin bis(mercaptoethyl tall oil fatty acid ester), dibutyltin bis(lauryl mercaptide), mercaptoethyl tall oil fatty acid ester), dimethyltin bis(mercaptoethyl butyl succinate ester), dimethyltin bis(2-mercaptoethyl caprylate), dimethyltin bis(2-mercaptoethyl stearate), dioctyltin bis( 2-mercaptoethyl caprylate),
Dimethyltin bis(2-mercaptoethyl oleate), dimethyltin bis(2-hydroxy C _12-14 mixed alkyl mercaptide), dibutyltin bis(2-octanoyloxide dodecyl mercaptide), dioctyltin bis(2- lauroyl oxide dodecyl mercaptide), dioctyltin bis(isooctyl mercaptoacetate), dioctyltin bis(2-ethylhexyl mercaptoacetate), dioctyltin bis(dodecyl thioglycolate), dimethyltin bis(isooctyl mercaptoacetate), dimethyl Tin bis(isooctylmercaptopropionate), dimethyltin bis(monothioglycerin diacetate), bis(2-
methoxycarbonylethyl)tin bis(isooctylthioglycolate), bis(2-methoxycarbonylethyl)tinbis(2-ethylhexylthioglycolate), bis(2-butoxycarbonylethyl)tinbis(butylthioglycolate), Diorganotin mercaptides such as bis(2-methoxycarbonylethyl)tin bis(stearylthioglycolate); bis[dibutylmono(isooctoxycarbonylmethylenethio)tin] sulfide;
Bis[bis(2-methoxycarbonylethyl)tinisooctylthioglycolate] sulfide, bis(dimethyltin monoisooctylthioglycolate) sulfide, bis[dibutyltin(2-mercaptoethylcaprylate)]sulfide, bis[dioctyl Diorganotin mercaptides and sulfides such as tin (2-mercaptoethyl caprylate) disulfide; dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, bis(2- Organic tin mercaptocarboxylates such as methoxycarbonylethyl)tin thioglycolate, bis(2-methoxycarbonylethyl)tin mercaptopropionate, monomethyltin tris (stearyl mercaptide), monobutyltin tris (lauryl mercaptide) ,
Monobutyl monochlorotin bis (lauryl mercaptide), monooctyltin tris (mercaptoethyl tall oil fatty acid ester), monobutyltin tris (mercaptoethyl tall oil fatty acid ester), monomethyltin tris (mercaptoethyl butyl succinate ester) ), monomethyltin tris (mercaptoethyl tall oil fatty acid ester), monomethyltin tris (nonanoyloxyethyl mercaptide), methyltin tris (2-mercaptoethyl laurate), monomethyltin tris (2-mercaptoethyl caprylate) ), monomethyltin tris (2-mercaptoethyl stearate), monomethyltin tris (2-mercaptoethyl stearate), monomethyltin tris (2-mercaptoethyl stearate), monomethyltin tris (2-mercaptoethyl stearate),
mercaptoethyl acetate), monomethyltin tris (2-mercaptoethyl oleate), monobutyltin tris (2-mercaptoethyl caprylate), monooctyltin tris (2-mercaptoethyl caprylate), monomethyl monochlorotin bis (2- mercaptoethyl caprylate),
Monomethyltin tris (2-lauroyloxide dodecyl mercaptide), monobutyltin tris (2-lauroyloxide dodecyl mercaptide)
-hydroxydecyl mercaptide), monomethyltin tris (monothioglycerin diacetate),
Monobutyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), monomethyltin tris (isooctylmercaptoacetate),
Monobutyltin tris (isooctyl mercaptopropionate), monooctyltin tris (dodecylthioglycolate), 2-methoxycarbonylethyltin tris (butylthioglycolate), 2
- Monoorganotin mercaptides such as butoxycarbonylethyltin tris(stearylthiopropionate) and 2-methoxycarbonylethyltintris(isooctylthioglycolate); bis[monobutyl di(isooctoxycarbonylmethylenethio)tin] ] Sulfide, bis[(2-methoxycarbonylethyl)tin bis(isooctylthioglycolate)] Sulfide, bis[methyltin bis(isooctylthioglycolate)]disulfide, bis(methyltin diisooctylthioglycolate) Trisulfide, bis(butyltin diisooctylthioglycolate) trisulfide, bis[methyltin di(2-mercaptoethyl thyl caprylate)] sulfide, bis[methyltin di(2-mercaptoethyl caprylate)] disulfide, etc. Examples include organic tin mercaptides and sulfides. The carboxylic acids constituting the aluminum carboxylate used in the present invention include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, and undecane. acid,
Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12
-Hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tert-
Butylbenzoic acid, dimethylhydroxybenzoic acid,
3,-5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid,
Acetoxybenzoic acid, salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid,
Examples include linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid. The organic phosphoric acids constituting the aluminum organic phosphate include monoorganic phosphoric acid and diorganic phosphoric acid, and examples of these organic groups include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl,
tridecyl, _C12-15 mixed alkyl, stearyl,
Alkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexylbenzyl, β-phenylethyl, γ-phenylpropyl, β-phenylpropyl, phenyl, naphthyl, tolyl, xylyl, ethylphenyl, butylphenyl, Examples include aryl groups such as 3-butylphenyl, octylphenyl, isooctylphenyl, tertiary-octylphenyl, nonylphenyl, and 2,4-di-tert-butylphenyl. Other additives commonly added to chlorinated vinyl chloride resins can also be added to the compositions of the present invention. Other compounding agents include organic acid salts of group metals, organic tin carboxylates, organic phosphite compounds, epoxy compounds, ultraviolet absorbers, quenchers, crosslinking agents, pigments, fillers, blowing agents, antistatic agents, Antifogging agents, plate-out prevention agents, surface treatment agents, lubricants,
Examples include flame retardants, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradants, processing aids, mold release agents, and reinforcing agents. The present invention will be explained in more detail with reference to specific examples below, but the present invention is not limited to these examples. Example 1 Using the following formulation, rolled at 190°C and then 180°C.
Press to create a test piece, initial coloring, 190℃
Thermal stability was measured at We also conducted a mill heat resistance test at 190°C. Furthermore, Izod impact strength was measured. The results are shown in Table-1. Compounded chlorinated vinyl chloride resin 100 parts by weight (Nica Temp T-380; manufactured by Nippon Carbide Co., Ltd.) Impact resistance modifier 5 (Kane Ace B-12; manufactured by Kanebuchi Chemical Co., Ltd.) Polyethylene wax 2 Dibutyltin bis (isooctylthioglyco) rate) 3 Aluminum compound 1

[Table] *1 Kyowa Chemical Hydrotalcite Example 2 A test similar to Example 1 was conducted using the following formulation. The results are shown in Table-2. Compound Chlorinated vinyl chloride resin 100 parts by weight Impact modifier 5 Polyethylene wax 2 Aluminum stearate 1 Organotin compound 3

【table】

[Table] Example 3 A test similar to Example 1 was conducted using the following formulation. In addition, the tensile strength and elongation of the test piece after 360 hours of irradiation were measured using a weatherometer, and the ratio to the original, that is, the residual rate was measured. The results are shown in Table-3. Compounded chlorinated vinyl chloride resin 50 parts by weight (Nicatemp T-380; manufactured by Nippon Carbide Co., Ltd.) Vinyl chloride resin 50 Impact resistance modifier 10 (Kane Ace B-22; manufactured by Kanebuchi Chemical) Ethylene bisstearylamide 0.3 Polyethylene wax Tux 0.7 Dibutyltin bis(isooctylthioglycolate) 3 Aluminum compound 1

【table】

Claims (1)

[Claims] 1 For 100 parts by weight of chlorinated vinyl chloride resin, (a)
0.01 to 10 parts by weight of an organotin mercaptide compound and
(b) A stabilized chlorinated vinyl chloride resin composition containing 0.01 to 10 parts by weight of at least one aluminum compound selected from aluminum carboxylates, aluminum organic phosphates, aluminum hydroxide, and hydrotalcites. thing.