JPS5948021B2 - Halogen-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin composition stabilized by containing a metal organic salt compound and a thioester-S-triazine compound.

Specifically, a stabilized halogen-containing resin composition characterized by adding (a) at least one selected from metal organic salt compounds and (b) a thioester-containing 5-triazine derivative to a halogen-containing resin. It is related to.

In general, halogen-containing resins have poor stability against heat and light, and tend to undergo thermal decomposition mainly due to dehydrohalogenation during thermoforming.

This causes a decline in the mechanical properties and color tone of processed products, resulting in significant disadvantages. Therefore, in order to avoid such drawbacks, it has been necessary to add one or more kinds of thermal stabilizers to the resin to suppress thermal deterioration during processing steps. Many metal soaps are used for this purpose,
As a result, almost satisfactory results were obtained in terms of thermal stability. However, among these metal soaps, cadmium soap, lead soap, etc. are highly toxic, and their use is currently largely restricted. It is therefore necessarily necessary to use cadmium or lead soaps or non-metallic stabilizers to obtain satisfactory thermal stability. For this purpose, methods have been considered in which two or more types of non-toxic metal soaps or combinations thereof and non-metal stabilizers are used to achieve a synergistic effect. However, although a certain degree of thermal stability can be obtained using such a method, the thermal stabilizing effect is considerably inferior to that when using cadmium or lead soap, and additional drawbacks arise, and the above-mentioned disadvantages arise. The method is insufficient to satisfy the technical problem as a stabilizer.

For example, the combination of a metal soap such as calcium, zinc, magnesium or barium with a polyhydric alcohol, diphenylthiourea or trisnonylphenyl phosphite,
The stabilizing effect is insufficient and cannot be put to practical use.

Although the combination of the metal soap and epoxidized soybean oil has a certain degree of heat stabilizing effect, it has the disadvantage of lowering the softening point of the resin when it is hard compounded. Furthermore, aminocrotonic acid esters have very poor compatibility with halogen-containing resins, and are particularly insufficiently effective against vinyl chloride resins obtained by suspension polymerization. Furthermore, although dehydroacetic acid improves the initial coloration, it does not have a long-term stabilizing effect. Moreover, it cannot be said that it is practically sufficient during molding.

For example, in the calender roll method, a plate-out phenomenon occurs on the surface of the roll, which impairs the surface shape of the molded product and significantly reduces processing efficiency. This plate-out phenomenon is observed in almost the same way in processing steps other than the calendar roll method, and is a drawback when halogen-containing resins are stabilized using metal soaps. Furthermore, with recent advances in processing technology for halogen-containing resins, there is a strong demand for excellent non-toxic stabilizers that prevent thermal decomposition during molding at high temperatures, and there is a need for stabilizers that can withstand harsh working conditions throughout various molding processes. is necessary.

In order to meet this demand, less toxic dioctyltin compound-based or dimethyltin-based stabilizers have been developed and put into practical use, but problems remain in long-term workability during molding. In view of the above facts, the present inventors have conducted extensive research and study over many years in order to develop a halogen-containing resin composition that has good thermal stability, good transparency, and initial colorability. has been reached. That is, the present invention is formed by adding (a) at least one selected from metal organic salt compounds and (b) a thioester-containing -S-triazine compound represented by the following general formula [1] to a halogen-containing resin. The present invention provides a stabilized halogen-containing resin composition.

(In the above formula, R represents alkyl, aryl, alkylaryl, halogenated aryl, hydroxyaryl, arylalkyl, cycloalkyl, or cycloalkene,
R and R2 are alkyl, aryl, alkylaryl, alkoxyl, phenoxy, halogen atom, mercapto, piperidino, R3morpholino, -N<, -NH-
R5 or -SCR゛ R4゛
11 is shown.

R3, R4 and R5 represent alkyl, aryl, alkylaryl, halogenated aryl, hydroxyaryl, arylalkyl, and cycloalkyl. ) The details of the present invention will be specifically explained below.

Specific examples of the alkyl group constituting the triazine compound represented by the above general formula [1] according to the present invention include the following.

That is, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, Sec-butyl, amyl, isoamyl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, These include lauryl, detradecane, hexadecane, and stearyl. Further, examples of the aryl group include phenyl, tolyl, naphthyl, etc., and examples of the alkylaryl group include:
Methylphenyl, dimethylphenyl, ethylphenyl,
Examples of the arylalkyl group include phenylmethyl, phenylethyl, phenylpropyl, and phenylisopropyl. Examples of the cycloalkyl group include cyclopropyl and cyclobenzene. Examples include cyclohexyl and cyclooctyl, and examples of the cycloalkene group include cyclohexene.

Further, examples of the alkyl moiety of the alkoxy group in R1 and R2 include the alkyls mentioned above.

Examples of the halogen atom include chlorine, bromine, and iodine atoms. Piperidino also includes those substituted with alkyl, such as methylpiperidino.

Examples of metal organic salt compounds in the present invention include metal carboxylates, phenolates, and organic tin salts. Carboxylates are metal salts of carboxylic acids, and phenolates are metal salts of phenols.

Examples of metals constituting these metal salts include Li,
There are K, Mg, Ca, Sr, Ba, Zn, Sn, etc.
Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, natonic acid, hydrofurylic acid, neoacid, 2-ethylhexylic acid, pelargonic acid, hydropuric acid, undecanoic acid, and lauric acid. acid, tridecanoic acid,
Myristic acid, palmitic acid, isostearic acid, stearic acid, 1,2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-T
ert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid,
Cumic acid, n-propylbenzoic acid, aminobenzoic acid, N
, N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, P-Tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, etc. , oxalic acid, malonic acid, succinic acid, geltaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid,
Examples include monoester or monoamide compounds of divalent carboxylic acids such as thiodipropionic acid, and di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanoic acid, pyromellitic acid, and mellitic acid. The phenols for obtaining the above phenolates include, for example, tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, leafylphenol, isoamylphenol, and ethylphenol. , isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, methyl - Tert-octylphenol and the like can be used.

Further, organic tin salts include monoorganic tin salts and diorganic tin salts, and specifically include the following.

That is, methyl stanoitsucic acid, butyl stanoitsucic acid,
Octyl stanoitsuccinic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, synchrohexyltin sulfide, monobutyltin oxide/sulfide methylthiostanoitsuccinic acid, butyl thiostanoic acid Neutschic acid, octylthiostanoitsuccinic acid, dibutyltin laurate, dibutyltin stearate, dioctyltin diolate, dibutyltin diolate, dibutyltin basic laurate, dibutyltin dicrotonate, dibutyltin bis(butoxydiethylene glycol malate), dibutyltin Dimethacrylate, dibutyltin disinnamate, dioctyltin bis(oleyl maleate), dibutyltin bis(stearyl maleate), dibutyltin itaconate, dioctyltin maleate, diamyltin bis(cyclohexyl maleate), dimethyltin dicrotonate, diethyltin bis( isooctylcytofuconate), dipropyltin bis(benzyl maleate), diisobutyltin bis(propyl maleate), zincro\xyltin maleate, dioctyltin bis(butyl maleate),
dibutyltin dimethoxide, dibutyltin dilauroxide,
Dioctyltin ethylene glycooxide, pentaerythritol, dibutyltin oxide condensate, dibutyltin bis(lauryl mercaptite), dimethyltin bis(stearyl mercaptite), monobutyltin tris(lauryl mercaptite), dibutyltin-β- Mercaptopropionate, dioctyltin-β-mercaptopropionate,
Dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate)
Dibutyltin bis(isooctylmercaptoacetate)
, dioctyltin bis(isooctyl mercaptoacetate), dioctyltin bis(2-ethylhexyl mercaptoacetate), dimethyltin bis(isooctyl mercaptoacetate), dimethyltin bis(isooctyl mercaptopropionate), monobutyltin tris(isooctyl mercaptopropionate) bis[monobutyldi(isooctoxycarbonylmethylenethio)tin]sulfide, bis[dibutylmono(isooctoxycarbonylmethylenethio)tin]sulfide monobutylmonochlortin bis(isooctylmercaptopropionate),
Monobutyl monochlorotin bis (isooctyl mercaptoacetate), monobutyl monochlorotin bis (lauryl mercaptite), dibutyl tin bis (ethyl celsol pumarate), bis (dioctyl tin laurate) malate, bis (dioctyl tin butyl maleate) malate , bis(methyltin diisooctylthioglycolate) disulfide, bis(methyl/dimethyltin mono/diisooctylthioglycolate) disulfide, bis(methyltin diisooctylthioglycolate) trisulfide,
Bis(butyltin diisooctylthioglycolate) trisulfide, 2-methoxycarbonylethyltin tris(butylthioglycolate), 2-methoxycarbonylethyltin tris(isooctylthiopropionate),
2-Ptoxycarbonylethyltin tris (stearylthiopropionate), 2-methoxycarbonylethyltin tris (isooctylthioglycolate), 2-methoxycarbonylpropyltin tris (octylthioglycolate), 2-methoxycarbonylethyl Tin Tris (2-
ethylhexylthiopropionate), 2-methoxycarbonylethyltin sulfide polymer 2-ethoxycarbonylpropyltin sulfide polymer 1, 2-ptoxycarbonylethyltin sulfide polymer 1, 2-isoproboxycarbonylethyltin sulfide polymer Polymer-1, bis(2-methoxycarbonylethyl)tin bis(isooctylthioglycolate), bis(comethoxycarbonylethyl)tinbis(2-ethylhexylthioglycolate), bis(methoxycarbonylethyl)tinbis(
2-ethylhexylthiopropionate), bis(2-
Prtoxycarbonylethyl)tin bis(butylthioglycolate), bis(2-methoxycarbonylethyl)tinbis(stearinorthioglycolate), bis(2-ethoxycarbonylpropino(c)tin bis(laurylthioglycolate) ), bis(2-isopropoxycarbonylethyl)tin bis(isooctylthiopropionate, bis(2-methoxycarbonylethyl)tin sulfide polymer, bis(2-methoxycarbonylpropyltin sulfide polymer), bis( 2-propoxycarbonylethyl) tin sulfide polymer bis(comethoxycarbonylethyl) tin sulfide polymer 1, bis(2-methoxycarbonylethyl) tin maleate polymer 1, bis(2-methoxycarbonylethyl) tin sulfide polymer
-Ethoxycarbonyl ethinotritin dilaurate, bis(
Examples include 2-methoxycarbonylisopropoxy)tin dilaurate, bis(2-methoxycarbonylethyl)tin bis(isooctylmalate), and the like. Next, the amounts of each of the above compounds added will be described.

It is preferable that the metal organic salt compound be used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the halogen-containing resin. Further, the thioester-S-triazine compound represented by the general formula [1] is preferably used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the resin. If the amount used is less than this, no significant effect will be obtained, and if it is more than this, no effect commensurate with the amount added can be expected. A more preferred range of the triazine compound is 0.05 to 3.0 parts by weight. The above general formula [
The thioesteno-S-triazine compound represented by 1] is a mercapto-S-triazine compound and a carboxylic acid chloride combined with a hydrogen chloride scavenger (e.g. triethanolamine).
It is easily synthesized by reaction in an organic solvent such as dioxane in the presence of .

Next, a specific example will be shown.

Next, to explain the halogen-containing resin in the present invention, the following are mentioned as specific examples.

For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, hydrogenated polyethylene, chlorinated rubber,
Vinyl chloride monovinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride monovinylidene chloride copolymer, Vinyl chloride-styrene monomaleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride monochlorinated propylene copolymer, Vinyl chloride monovinylidene chloride monovinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-metatalylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer Polymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-13-methylbutene, ethylene monovinyl acetate copolymers, ethylene-propylene copolymers, etc. polyolefins and copolymers thereof,
Polystyrene, acrylic resin, styrene and other monomers (
copolymers with maleic anhydride, butadiene, acrylonitrile, etc., acrylonitrile-butadiene-
Styrene copolymer, acrylic acid ester-butadiene-
Examples include styrene copolymers, methacrylic acid ester-butadiene-styrene copolymers, blends of these resins, block copolymers, graft copolymers, and the like. The halogen-containing resin composition of the present invention may contain a phthalate ester plasticizer or other ester plasticizer, phosphate ester plasticizer, epoxy plasticizer, chlorine plasticizer, or other plasticizer depending on the purpose. Can be used as appropriate. Furthermore, it goes without saying that other additives may be added to the composition of the present invention to further improve its performance. Examples of these other additives include antioxidants, light stabilizers, etc. agent, nucleating agent, filler, epoxy stabilizer,
Organic chelator, pigment, antistatic agent, antifogging agent, plate-out prevention agent, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifog agent, bactericide, photodegrading agent, nonmetallic stabilizer, boric acid ester , processing aids, mold release agents, and the like.

As these other additives, conventionally well-known compounds can be used. For example, as antioxidants, phenol-based, amine-based, phosphite-based, and sulfur-based antioxidants are used. The one disclosed in Japanese Patent No.-78692 is used.

As the light stabilizer, benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, various metal salts or metal chelates, triazine-based, and piperidine-based light stabilizers can be used.
The material disclosed in Japanese Patent No. 9-78692 can be used. The present invention will be specifically explained below using Examples.

However, the invention is not limited to the examples listed below. In the examples, the initial coloring property indicates the degree of yellowness measured by a solder colorimeter.

Example 1 In order to examine the stabilizing effect of the composition of the present invention, samples were prepared by calendering and heat press processing according to the formulation, and the thermal stability was determined by a heat aging tester at 190°C and by heat press processing. Transparency and initial coloration were measured.

The results are shown in Table 1. of? Example 2 In order to examine the excellent stabilizing effect of the composition of the present invention, a performance test was conducted in the same manner as in Example 1 using the following formulation.

The results obtained are shown in Table 2 below. Example 3 In order to examine the stabilizing effect of the compound according to the present invention on a polyvinyl chloride-acrylonitrile-butadiene-styrene copolymer (ABS resin) blend product, a sample was prepared using the same procedure as in Example 1 with the following formulation. I conducted a test.

The results are shown in Table 3 below. Example 4 In order to examine the stabilizing effect of the composition of the present invention, a performance test was conducted in the same manner as in Example 1 using the following tin formulation.

The results are shown in Table 4. Example 5 Next, the same test as in Example 1 was conducted by adding other additives to the composition of the present invention and examining the effects of their combined use.

The results are shown in Table 5 below. <Blend> Polyvinyl chloride resin di-2-ethylhexyl phthalate 100 parts by weight 48 Eboxidized soybean oil 2.011C a-benzoate Mg-stearate Zn-stearate sample (Table 5) Other additives (Table 5) Table) 0.7 parts by weight 0.7110. 7110. 5p0.3p Also, talc, asbestos, calcium carbonate, clay,
The thioester-containing S-triazine according to the present invention is added as a stabilizer to a polyvinyl chloride resin composition containing a filler such as titanium white and a polyvinyl chloride resin composition containing a pigment such as aluminum heum powder, copper powder, or bronze powder. Compositions with added compounds and metal salts showed excellent stabilizing effects.

Claims (1)

[Claims] 1. A stabilized compound obtained by adding (a) at least one metal organic salt compound and (b) a thioester-containing S-triazine compound represented by the following general formula [I]. Halogen-containing resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕(In the above formula,
R is alkyl, aryl, alkylaryl, halogenated aryl, hydroxyaryl, arylalkyl,
Represents cycloalkyl or cycloalkene, R_1 and R_2 are alkyl, aryl, alkylaryl, alkoxyl, phenoxy, halogen atom, mercapto,
Indicates piperidino, morpholino, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NH-R_5 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_3, R_4 and R_5 represent alkyl, aryl, alkylaryl, halogenated aryl, hydroxyaryl, arylalkyl or cycloalkyl. )2 The composition according to claim 1, wherein the metal organic salt compound is a carboxylate. 3. The composition according to claim 1, wherein the metal organic salt compound is a phenolate. 4. The composition according to claim 1, wherein the metal organic salt compound is an organic tin salt. 5. The composition according to claim 1, 2, 3, or 4, wherein R in the general formula [I] is phenyl. 6. The composition according to claim 1, 2, 3, or 4, wherein R in the general formula [I] is alkyl. 7 In general formula [I], R_1 is ▲mathematical formula, chemical formula,
The composition according to claim 1, 2, 3, 4, 5, or 6, which has a table, etc.