JPH0571626B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) This invention relates to a stabilized chlorine-containing resin composition. More specifically, the present invention provides a chlorine-containing resin containing one or more low-toxicity or non-toxic organometallic salt compounds, an organic phosphite compound,
The present invention relates to a chlorine-containing resin composition which contains a 2-mercaptopyridine-1-oxide compound in combination and has excellent anti-coloring properties against thermoforming and long-term high-temperature heat storage. (Prior art) Chlorine-containing resin compositions have excellent physical and chemical properties, and can be changed from hard to soft, from transparent to colored to opaque, by adding a plasticizer and increasing or decreasing its amount. It is extremely useful and can be applied to various molded products. However, this chlorine-containing resin composition can cause decomposition accompanied by dehydrochlorination if it is affected by heat during thermoforming or if it is exposed to high temperatures for a long time as a molded product after processing. This has the disadvantage that it causes discoloration and deterioration of the physical properties of the molded article, resulting in a significant decrease in the physical properties and commercial value of the molded article. For this reason, various methods of heat stabilization by adding non-toxic or low-toxicity stabilizers have been conventionally employed. For example, Ba-Zn or
This is a method of stabilizing a chlorine-containing resin by adding a stabilizer, which is a combination of Ca-Zn metal soap, a hindered phenol antioxidant, and an epoxy compound, to the chlorine-containing resin. It is true that these stabilizer components pose no problems in terms of toxicity, but they are inferior in terms of preventing discoloration during thermoforming, and there has been a demand for improved performance in this aspect. For this reason, methods have been proposed in which other stabilizing aids are used in combination. For example, the present applicant previously proposed a method in which a β-diketone compound is used in combination as a coloring inhibitor in Japanese Patent Publication Nos. 52-47948 and 57-9386, and a method in which a metal complex salt of β-diketone is used in Japanese Patent Publication No. 57-39260. Method and Special Publication 1986-
No. 44899 proposed a method using a keto-acetonitrile compound. However, methods using these β-diketone compounds in combination,
It is still difficult to say that it is sufficient to prevent discoloration of molded products under conditions where they are exposed to high temperatures for a long period of time. Separately, US Pat. No. 3,533,993 discloses that 2-mercaptopyridine-
A method of thermal stabilization by adding 1-oxide and its metal compounds is disclosed. In this method, only a 2-mercaptopyridine-1-oxide compound is added as a stabilizer to a plastil sol composition of polyvinyl chloride without using metal soap, but this method also does not have the effect of preventing coloration. It is extremely small, and it is therefore impossible to expect it to be stable enough to withstand high heat during severe processing. Furthermore, molded articles of chlorine-containing resin compositions have recently been widely used as interior parts for automobiles and other vehicles, and are often used in the form of integral foams with soft urethane foam for seat sheets, head rests, and the like. In such cases, these vehicle interior parts may be exposed to high temperatures ranging from 80°C to a maximum of 140°C for long periods of time, depending on the usage conditions of the vehicle. In such a case, there is a drawback that the amine compound remaining in the polyurethane foam migrates into the chlorine-containing resin composition molded article, resulting in a deterioration in the quality of the molded article. In order to cope with these severe conditions, various studies have been carried out, but so far nothing has been achieved that is necessarily satisfactory, and there has been a desire for something that can be expected to be even more effective. (Problems to be Solved by the Invention) This invention aims to stabilize against thermal deterioration when thermoformed under severe conditions, and to stabilize the processed chlorine-containing resin formed product when it is exposed to high temperatures for a long time. The object of the present invention is to obtain a thermally stabilized chlorine-containing resin composition that has an excellent preventive effect against thermal deterioration and coloration. (Means for Solving the Problems) That is, the present invention provides that 100 parts by weight of chlorine-containing resin
(a) 0.1 to 8 parts by weight of at least one or more organic carboxylic acids, phenolates, and alkyltin compounds of lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, or cerium; and (b) organic 0.01 to 3 parts by weight of a phosphite compound and (c) the following general formula

[Formula] (where M is a hydrogen atom, 2-thiopyridine-1-
oxide, lithium, sodium, potassium, magnesium, calcium, barium, zinc, antimony or tin, or n represents a number from 1 to 5. )
This is a stabilized chlorine-containing resin composition characterized in that it contains a combination of 0.001 to 3 parts by weight of a 2-mercaptopyridine-1-oxide compound represented by: This invention will be further explained below. The organometallic salt compound of the stabilizer component (a) constituting the composition of the present invention is a metal soap, and the metals constituting this metal soap include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, tin or is cerium,
The organic residues that bind to this metal include carboxylic acids and phenols. Carboxylic acids include saturated aliphatic or unsaturated aliphatic carboxylic acids having 4 to 22 carbon atoms, and 7 to 16 carbon atoms.
carbocyclic carboxylic acids, hydroxy acids and alkoxy acids having 2 to 10 carbon atoms, such as hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid , behenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid,
Linoleic acid, isostearic acid, 12-hydroxystearic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, pt-butylbenzoic acid,
Examples include pt-octylbenzoic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, atropic acid, fulric acid, thenic acid, nicotinic acid, salicylic acid, tartaric acid, acetoacetic acid, or a mixed carboxylic acid thereof. be able to. Also, carbon number 6-
Twenty-four phenols are also useful, such as phenol, cresol, xylenol, pt-butylphenol, pt-octylphenol, nonylphenol, dinonylphenol, decylphenol, and dodecylphenol. The organometallic compound bonded to these organic residues and the metal may be an acidic salt or a neutral salt, or may be a basic salt or an overbased salt in which a chemical equivalent or more of the metal is bonded. In addition, tin compounds are typified by alkyltin compounds, such as dimethyltin bis(isooctylthioglycolic acid ester) salt,
Dibutyltin dilaurate, dibutyltin maleate polymer, dibutyltin bis(monoalkyl maleate C2-C18 ester) salt, dibutyltin bis(isooctylthioglycolic acid ester) salt, dibutyltin thiopropionate, monooctyltin tris(isooctyltin) Examples include octyltin (isooctylthioglycolic acid ester) salt, monooctyltin tris(laurylthioglycolic acid ester) salt, dioctyltin maleate polymer, and dioctyltin (isooctylthioglycolic acid ester) salt. The above organometallic salt compounds may be used alone in the present invention, or the combination of zinc salt compounds and other metal salts, such as lithium, sodium, potassium, magnesium, calcium, barium salts, etc., can have a synergistic effect. It is preferable because it plays The amount of these organic metal salts added is 0.1 to 8 parts by weight, and even 0.5 parts by weight per 100 parts by weight of chlorine-containing resin.
~5 parts by weight is preferred. Examples of the organic phosphite compound used as the stabilizer component (b) in this invention include triphenyl phosphite, tricresyl phosphite, triisooctyl phosphite, tridecyl phosphite, tridecyl thiophosphite, and tridecyl phosphite. Benzyl phosphite, trisnonylphenyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, distearylbentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl penta Erythritol diphosphite, tris-2,4
-di-t-butylphenyl phosphite, 2,4
-di-t-butylphenyl diisodecyl phosphite, tris-4-oxy-2,5-di-t-butylphenyl phosphite, tris-butoxyethoxyethyl phosphite, tetratridecyl-
4,4'isopropylidene diphenyl diphosphite, tetratridecyl-4,4'-isopropylidene dicyclohexyl diphosphite, tetrakis phenyl dipropylene glycol diphosphite, peptoxyphenyl dipropylene glycol triphosphite, hexakis Dipropylene glycol tetraphosphite, tetraquinonylphenyl dipropylene glycol diphosphite,
Poly(dipropylene glycol) phenyl phosphite and the like. Also useful are organic phosphites in which one or two of the organic residues, such as alkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl groups, are replaced with hydrogen atoms. For example, diphenyl acid phosphite, phenyl acid phosphite, diisooctyl acid phosphite, diisodecyl acid phosphite, phenyl isooctyl acid phosphite, phenyl isodecyl acid phosphite, dibenzyl acid phosphite,
Acid phosphite compounds such as dinonyl phenyl acid phosphite can be mentioned. At least one of the above-mentioned organic phosphite compounds is used in the present invention, and the amount added is 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the chlorine-containing resin. Examples of the 2-mercaptopyridine-1-oxide compound used in the present invention include 2-mercaptopyridine-1-oxide, 2-mercaptopyridine-1-oxide lithium salt, 2-mercaptopyridine-1-oxide sodium salt, 2-mercaptopyridine-1-oxide
mercaptopyridine-1-oxide potassium salt,
2-mercaptopyridine-1-oxide magnesium salt, 2-mercaptopyridine-1-oxide calcium salt, 2-mercaptopyridine-1-oxide barium salt, 2-mercaptopyridine-1
-Zinc oxide salt, 2-mercaptopyridine-1
-antimony oxide () and () salt, 2-
Mercaptopyridine-1-oxide tin ()
salt, 2-mercaptopyridine-1-oxidebutyltin salt and 2,2'-dithiobis(pyridine-
1-oxide). The amount of the 2-mercaptopyridine-1-oxide compound added is 0.001 to 3 parts by weight, preferably 0.005 to 0.5 parts by weight, per 100 parts by weight of the chlorine-containing resin. As mentioned above, the chlorine-containing resin composition of the present invention is
Containing the three stabilizer components (a) to (c) described above is an essential component, and the synergistic effect of these stabilizers not only during thermoforming processing but also when exposed to high temperatures for long periods of time. It shows excellent effects in preventing thermal deterioration and coloring. In addition, the present invention further includes the following stabilizing aids or other additives, such as β-diketone compounds, inorganic metal salt compounds, antioxidants, epoxy compounds, and other known compounds. be able to. Examples of the β-diketone compound here include benzoylacetone, dibenzoylmethane,
Compounds such as tribenzoylmethane, lauroylbenzoylmethane, myristoylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, 4-methoxybenzoylbenzoylmethane, 4-chlorobenzoylbenzoylmethane, dehydroacetic acid, and the above β-diketone compounds, zinc, and barium. , a metal complex salt combined with a metal such as calcium or an alkyltin.
Inorganic metal salt compounds include sodium, potassium, magnesium, calcium, barium,
Oxides, hydroxides or inorganic acid salts of metals selected from the group of zinc, aluminum, silicon, etc., such as phosphates, phosphites, silicates, acetates, nitrites, sulfates, nitrites , chlorate, perchlorate, borate or basic inorganic salt. These inorganic metal salts may be a mixture or a double salt, and examples thereof include calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, A-type, X-type, Y-type mainly composed of zinc borate, sodium silicate, magnesium silicate, aluminum sulfate, sodium aluminum sulfate, synthetic hydrotalcites, wollastonites, tobermolites, and aluminosilicate. Examples of synthetic zeolites include: As antioxidants, there are hinted phenols such as alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenols or sulfur-containing alkanoic acid alkyl esters, such as 2,6-di-t- Butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-
t-butylphenol), 4,4'-thiobis-(6
-t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, and dilaurylthiodipropionate, distearylthio These include dipropionate ester. Metal salts of phosphate esters are also useful as heat-stable additives, such as magnesium, calcium, barium, zinc or dibutyltin salts of mono- and diisooctyl phosphates, magnesium, calcium, barium, zinc or dibutyltin salts of mono- and diisodecyl phosphates. salts, mono- and ditridecyl phosphates of magnesium, calcium,
Mention may be made of barium, zinc or dibutyltin salts, sodium, magnesium, calcium, barium or zinc salts of mono- and distearyl phosphates, magnesium, calcium, barium or zinc salts of mono- and diphenyl phosphates, and the like. Examples of epoxy compounds include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives, such as epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, and epoxidized Butyl linseed oil fatty acid, alkyl esters such as butyl epoxy stearate or 2-ethylhexyl, 3-(2-xenoxy)-1,2-epoxypropane, epoxy polybutadiene, bisphenol-A-diglycidyl ether, 3,4-
Epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate and the like. Other stabilizing aids include polyhydric alcohols such as bentaerythritol, diventaerythritol, mannitol, and sorbitol, ester compounds of these polyhydric alcohols with aliphatic monohydric or polycarboxylic acids, amino acids, and other compounds. β-aminocrotonic acid alkyl ester, tris(hydroxyalkyl), which is a nitrogen-based compound
Isocyanurates, benzotriazole-based light stabilizers, hindered amine-based stabilizers, such as 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-
di-t-butyl-2-hydroxyphenyl)-5
-chlorobenzotriazole, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly{[6-(1,1,3,3 -tetramethylbutyl)imino-1,3,5-triazine-
2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]}, 2( 3,5-di-t-butyl-4
-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4
-piperidyl). Further, as a processing agent, organic phosphate ester compounds such as nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid, dodecylphenoxypolyethoxyphosphoric acid, octylphenoxypolyethoxyphosphoric acid, etc. can be mentioned. can. The above-mentioned stabilizing aids can be used as appropriate for the purpose of further improving thermal stability, light resistance, or processability. Examples of the chlorine-containing resin in the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-urethane copolymer, and chlorinated polyethylene. , chlorinated polypropylene, or blends of these chlorine-containing resins with urethane polymers, acrylonitrile-butadiene-styrene copolymers, or methacrylic acid ester-butadiene-styrene copolymers. The chlorine-containing resin composition of the present invention can provide a wide range of molded products, from hard to soft, by changing the amount of plasticizer, for example, additives such as phthalate ester, depending on the purpose of the molded product. Further, fillers, pigments, antistatic agents, antifogging agents, flame retardants, fungicides, crosslinking agents, foaming agents, processing aids, and the like may be used in combination as necessary. Next, the present invention will be further explained based on examples. Example 1 A composition prepared by blending each stabilizer component shown in Table 1 with 100 polymerized parts of polyvinyl chloride resin (degree of polymerization 1100) was kneaded for 5 minutes with a kneading roll heated to 180°C, and then the thickness was determined. A uniform sheet of 0.3 mm was formed.
The following two types of tests 1 and 2 were conducted using this original sheet. The results of these two tests are shown together in Table 1. Test 1 A test piece was made from the original sheet and placed in a gear oven aging tester heated to 185°C for a certain period of time to examine the time until coloring and black decomposition due to thermal deterioration. The results are shown in the Test 1 column of Table 1. Test 2 A test piece similar to Test 1 was made from the original sheet, 8 pieces were stacked on a mold, and heated at 185℃ using a press molding machine.
Pressure molding was carried out at 150 kg/cm ² for 10 minutes. The resulting coloration and degree of transparency were examined. The results are shown in the Test 2 column of Table 1. In addition, as a comparative example, the 2-thiopyridine-1-oxide compound of (1-1) of the comparative example lacking the 2-thiopyridine-1-oxide compound of (c) which is an essential requirement in the composition of the present invention is included. Comparative examples (1-2 to 1-4) lacking other essential components of
Tests were also conducted on the following, and the results are shown in the same table. Among the comparative examples, (1-3) is one in which a lubricant was further added.

[Table] As is clear from Table 1, the products of the present invention had good results in both Tests 1 and 2. That is, there is no initial coloring or coloring after 20 minutes, and the time until decomposition is 70 to 75 minutes. Furthermore, the results of Test 2 were also good. On the other hand, all of the comparative examples were slightly yellowish in the original sheet stage and turned reddish after 20 minutes. The decomposition time is also fast at 60 minutes and 40 minutes. Furthermore, Comparative Example 1-
2. In 1-4, it is not even possible to obtain the original sheet itself. In Comparative Example 1-3, a lubricant was added and an original sheet was made, but when this sheet was left at room temperature for 24 hours, oily and powdery substances seeped out on the surface, and the transparency deteriorated over time. It has gotten worse. Furthermore, in Test 2, initial coloring was observed in the comparative example. The difference between the comparative example product and the present invention is obvious. Example 2 Various metal salts were used as component (c) of the stabilizer components (a) to (c) of the present invention, and a known stabilizing aid was further used in combination. These various metal salts and stabilizing aids are shown in Table 2. The formulation was as follows, and a sheet was prepared under the same conditions as in Example 1. In addition, for Tests 1 and 2 regarding this sheet, Example 1
I did the same thing. The results are shown in Table 3. (Composition) Polyvinyl chloride (degree of polymerization 1100) 100 parts by weight Dioctyl phthalate 30 Epoxidized soybean oil 2 Barium stearate 0.4 Overbased barium dodecyl phenolate
0.6 〃 Carbonate complex zinc stearate 0.3 〃 Zinc pt-butylbenzoate 0.3 〃 Tetratridecyl-4,4'-isopropylidene diphenyl diphosphite 0.8 〃

【table】

[Table] As is clear from the results in Table 3, the original sheets were all uncolored and had good transparency. In Test 1, there was no initial coloration at 15 minutes, and coloration at 45 minutes was only slightly yellow to yellow, and did not reach red. Black decomposition also took 70 to 120 minutes, and good results were obtained in both cases. The press in Test 2 also had good transparency. Example 3 In this example, the thermal stability of an integral composite molded article with polyurethane foam was investigated. The formulation of the composition is as follows. Moreover, the integral molding of the vinyl chloride resin sheet and polyurethane fluor was performed as follows. (Compound disposal) Polyvinyl chloride (degree of polymerization 1300) 100 parts by weight Dialkyl ( _C9 - _C11 ) phthalate 30 Epoxidized soybean oil 10 ABS 30 NBR 15 Barium stearate 0.8 Barium nonylphenol 1.0 Lauric acid Zinc 0.3 〃 Poly(dipropylene glycol) phenyl phosphite 0.8 〃 Other stabilizer components (c) and other stabilizing aids
As described in Table 4 (integral molding method with polyurethane foam) 90 parts by weight of EP-3033 (trade name of Mitsui Toatsu Chemical Co., Ltd.) as polyol, 8 parts by weight of triethanolamine, 0.5 parts by weight of triethylenediamine, and 1.5 parts by weight of water. A urethane foaming stock solution was prepared by mixing 70 parts by weight of MDI-CR (trade name, Mitsui Toatsu Chemical Co., Ltd.) as an isocyanate with thorough stirring. This was injected onto the roll-milled vinyl chloride resin sheet with a thickness of 0.5 mm and foamed to form a urethane foam with a thickness of 20 mm and an integrally molded product with the vinyl chloride sheet. This material was used as an original sheet and placed in a gear open aging tester heated to a constant temperature for a certain period of time to examine the state of thermal deterioration. The results are shown in Table 4. Also,
After a certain period of time had elapsed, the molded product was subjected to a physical property test according to JISK 7113-81 (Plastic tensile test method). The results are also shown in Table 4.

[Table] Note 2 Synthetic hydrotalcite compound manufactured by Kyowa Chemical Industry Co., Ltd. As is clear from the results in Table 4, all of the examples performed well in the coloring test due to thermal deterioration. In particular, the color was about yellow after 300 hours of testing at 120°C, which shows that it is very good. The results of the tensile test are similarly good.

Claims (1)

[Claims] 1 100 parts by weight of chlorine-containing resin contains (a) lithium, sodium, potassium, magnesium, calcium,
At least one or two or more of organic carboxylates, phenolates, and alkyltin compounds of strontium, barium, zinc, or cerium.
0.1 to 8 parts by weight, (b) 0.01 to 3 parts by weight of an organic phosphite compound, and (c) the following general formula
oxide, lithium, sodium, potassium, magnesium, calcium, barium, zinc, antimony or tin, or n represents a number from 1 to 5. )
A stabilized chlorine-containing resin composition characterized in that it contains a combination of 0.001 to 3 parts by weight of a 2-mercaptopyridine-1-oxide compound represented by: