JPS59113047A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition for suppressing fully coloring at the initial- middle periods, having improved heat stability, obtained by blending a chlorine- containing resin with a specific organometallic salt compound and a specified dicarbonyl compound. CONSTITUTION:A chlorine-containing resin is blended with at least one organometallic salt compound of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, and tin and a dicarbonyl compound shown by the formula (R is aryl replaced with halogen atom). A combination of a zinc salt and another metal salt (1:0.1-10) is preferable as the metallic salt compound. 2-(2- Chlorobenzoyl)-cyclohexanone, etc. is preferably used as the dicarbonyl compound. 100pts.wt. resin is blended with 0.05-10pts.wt., preferably 0.1-5pts.wt. metallic salt compound and 0.001-5pts.wt., preferably 0.01-3pts.wt. dicarbonyl compound.

Description

Detailed Description of the Invention The present invention is characterized by adding a low toxicity or non-toxic organic metal salt compound and an organic compound represented by the general formula (1) below to a chlorine-containing resin. The present invention relates to a stabilized chlorine-containing resin composition.

Chlorine-containing resins are subjected to various thermoforming processes depending on their purpose of use, but during such thermoforming processes, they tend to undergo thermal decomposition due to dehydrochlorination due to the influence of heat. For this reason, it is well known that deterioration in color tone of molded products causes deterioration in physical properties, resulting in a significant decrease in commercial value. Therefore, various stabilizers have been proposed and put into practical use in order to improve these drawbacks.

For example, (1) cadmium-barium, (2) cadmium-barium-lead, (3) cadmium-barium-zinc, (4) barium-zinc, or (5) calcium-zinc organometallic base compounds. Stabilizers are commonly used in combination with stabilizing aids such as, organic phosphoric acid esters, phenolic antioxidants or epoxy compounds. However, when a stabilizer consisting of a combination of the organic metal salts (1) to (3) and the above-mentioned stabilizing aid is used, almost satisfactory results in terms of thermal stability are obtained. However, there are drawbacks such as problems with working environment hygiene and toxicity in molded products. On the other hand, when using a low-toxicity or non-toxic stabilizer consisting of a combination of the organic metal salts (4) to (5), the above-mentioned stabilizing aid, and further aminocrotonic acid ester, the sanitary Although there are relatively no problems in terms of toxicity, the thermal stability during thermoforming processing is insufficient. Therefore, various stabilizers have been studied and proposed for the purpose of improving this problem.

For example, in Japanese Patent Publication No. 41-8786, the above (j C
When using a stabilizer consisting of an a-Zn organic metal salt and a ketoacetic acid compound, there are problems in terms of processability such as plate-out. A stabilizer consisting of a salt and a β-diketone compound was discovered as disclosed in Japanese Patent Publication No. 52-47948, Japanese Patent Publication No. 57-9386, etc., and a stabilizing method was proposed.Furthermore, The organic metal salts of (4) to (5) above;
Stabilizers consisting of metal complex salts of β-diketone compounds were discovered and proposed as disclosed in Japanese Patent Publication No. 57-39260.

However, when a stabilizer consisting of a combination of such a low-temperature or non-toxic organic metal salt, a β-diketone compound or a metal complex salt thereof, and a stabilizing agent is used, it can be fully satisfied in industrial practice. It cannot be said that obtaining a thermal stabilizing effect is a problem. For example, when a large amount of calcium carbonate or titanium oxide is blended into the resin and thermoforming is carried out, the effect of thermal stabilization, especially in suppressing discoloration in the early to middle stages, is not sufficient. In the past, there was a strong desire to improve thermal stability.

As a result of various studies to solve these technical problems, the present inventors have discovered a chlorine-containing resin composition that has excellent thermal stability, such as sufficiently suppressing discoloration in the early to middle stages, and has completed the present invention. This is what I did.

That is, the present invention provides a chlorine-containing resin, (c) at least one or two or more organometallic salt compounds of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin, and 0 the following general formula (formula wherein R represents an aryl group substituted with a rogen atom), and at least one of the specified carbonyl compounds, which is an organic compound represented by: It is a containing resin composition.

The organic metal salt compound as a component of the stabilizer used in the present invention is generally called a metal soap, and the organic residues constituting the metal soap include the following carboxylic acid and phenol residues.

Carboxylic acids include monocarboxylic acids and dicarboxylic acids of saturated or unsaturated fatty acids having 6 to 22 carbon atoms, and 6 to 22 carbon atoms.
~16 carbocyclic or hydroxy having 2 to 16 carbon atoms,
Alkoxy, oxocarboxylic or heterocyclic carboxylic acids, as well as aminocarboxylic acids, such as hexanoic acid, octanoic acid, 2-ethylhexylic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, no</L-mitic acid , stearic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid,
Rilunic acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, aladinic acid, tb
and benzoic acid, toluic acid, chlorobenzoic acid, p-tert-butylbenzoic acid, xylic acid, ethylbenzoic acid, p-octylbenzoic acid, co-phosphoric acid, glutaric acid. , adipic acid, pimelic acid, speric acid, azelaic acid, heptano(sinic acid, methacrylic/cyanoic acid, crotonic acid, isocrotonic acid, naphthoic acid, phthalic acid, isophthalic acid,
Terephthalic acid, cinnamic acid, hydroatrobic acid, glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, acetoacetic acid, levulinic acid, salicylic acid, anisic acid,
Cyclohexanoic acid, fulic acid, thenic acid, nicotinic acid, isonicotinic acid or mixed acids of these carboxylic acids. Further examples include alanine, methionine, aspartic acid, and glutamic acid.

Phenols having 6 to 24 carbon atoms are also useful as other organic residues, such as phenol, pyrocatechol, renlucinol, pyrogallol, cresol, p-1 tributylphenol, xylenol, p-octylphenol, nonylphenol, Examples include dinonylphenol, tesylphenol, and dodecylphenol.

In addition, soot compounds are typified by alkyltin compounds, such as dimethyltin laurate, dibutyltin laurate, dioctyltin laurate, dibutyltinsumarate polymer, dibutylsmalate alkyl ester salt, and dioctyltinsmaleate alkyl ester. salt, dimethylsuthioglycolic acid alkyl ester salt, dimethylsuthiopropionate, dibutylsuthioglycolic acid alkyl ester salt, dibuti,
Examples include rutin thioproprionate, dioctyltin thioglycolic acid alkyl ester salt, and dioctyltin thiopropionate.

However, the organometallic salt compound bound to such an organic residue may be an acidic salt or a neutral salt, or a basic or overbased salt having equimolar or more of the metal bound thereto.

(These organometallic salt compounds in the present invention may be used alone or may include zinc salts and other metal salts, such as barium, calcium, magnesium, strontium, lithium, potassium, sodium or soot metals.) A combination with salt is more preferred. In this case, the ratio of zinc salt to other metal salt is usually 1, O: weight ratio of 0.1 to 10, preferably 1.0 to 0.2 to 5.0. The organic metal salt compound is added in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the chlorine-containing resin.

General formula (1) of the constituent component 0 of the stabilizer used in the present invention
), i.e., dicarbonyl compounds, include 2i2-tribenzoyl)cyclohexanone, 2-(3-chlorobenzoyl)cyclohexanone, 2-(4-chlorobenzoyl)cyclohexanone,
-(2,4-dichlorobenzoyl)cyclohexanone,
2(2,5-dichlorobenzoyl)cyclohexanone,
2-(2,6-dichlorobenzoyl)cyclohexanone, 2-(3,4-dichlorobenzoyl)cyclohexanone, 2-(3,5-dichlorobenzoyl)cyclohexanone, 2-(2-phlorobenzoyl)cyclohexanone, 2-pentafluoro One example is benzoylcyclohexanone. The dicarbonyl compound mentioned above is 0.001 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.
It is added in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 3 parts by weight.

Therefore, the present invention provides a stabilized resin composition obtained by adding a stabilizer having two components (A-0) to a chlorine-containing resin, which has excellent thermal properties. Stability, especially suppressing and preventing early- to mid-term discoloration.

In addition to the above two components, the resin composition of the present invention also contains:
By adding a known stabilizer or stabilizing aid, thermal stabilization performance, processability, weather resistance, etc. are further improved.

Such useful stabilizers or stabilizing aids include organic phosphites such as trialkylphosphites, triarylphosphites, alkylaryl phosphites,
Examples include trialkyl phosphite, bisphenol A phosphite, and polyhydric alcohol phosphite. Typical compounds include triisooctyl phosphite, triisodecyl phosphite, triphenyl phosphite, diisodecyl sonophenyl phosphite, diphenylmonotecyl phosphite, tribenzyl phosphite, trinonylphenyl phosphite, 4.4
'-Isofurohylidene diphenyl alkyl (C12-C
15) Phosphite, poly(dipropylene glycol)
Phenylphosphite 1 Distearylpentaerythritol diphosphite, tris(4-oxy-3,5-
di-tert-butylphenyl) phosphite, heptakis (
dipropylene glycol) triphosphite, etc.

Furthermore, the above-mentioned organic phosphites are acid phosphites in which one or two of the organic residues such as alkyl, aryl or aralkyl are substituted with hydrogen atoms, such as diphenyl acid phosphite, diisodecyl acid phosphite, etc. These include phosphite, inthicylphenyl acid phosphite, dibenzyl acid phosphite, monophenyl acid phosphite, monotridecyl acid phosphite, and mononylphenyl acid phosphite.

Also, phosphonate compounds such as diisooctylphosphonate, dibenzylphosphonate, dilaurylphosphonate, distearylphosphonate, diphenylphospho*-h, phenylisodecylphosphonate, dibenzylphosphonate, dinonylphenylphosphonate, triphenylphosphonate, dinonylphenyl phosphonate,
Organic phosphorus compounds such as tribenzylphosphonate and trinonylphenylphosphonate.

Examples of phenolic compounds include alkylated phenol, alkylated phenol ester, alkylene or alkyritene hisphenol, polyalkylated phenol, and thiobisalkylated phenol. Butylated hydroxyanisole, 2,2'-methylenebis(
4-methyl-6-tert-butylphenol) 4,4'-thiobis(6-tert-butyl-m-cresol), and other antioxidants such as thiodipropionic acid alkyl ester.

Also, inorganic metal salt compounds, such as lithium, sodium, potassium, magnesium, calcium, barium,
Hydroxides, oxides or carbonates of metals selected from the group consisting of strontium, zinc, aluminum, indium and soot, as well as basic inorganic salts, such as phosphoric acid, phosphorous acid, silicic acid, Nitric acid, nitrous acid, sulfuric acid, sulfite, or boric acid and the above metal or a chloride, oxide, or hydroxide of the metal, or a mixture thereof.

Commonly used stabilizing aids as described below can be added to the resin composition of the present invention. An example is an epoxy compound, and typical compounds include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. Also, polyhydric alcohol compounds, such as pentaerythritol, dipentaerythritol, mannitol, sorbitol* Taha: Ester compounds of whitebait polyhydric alcohols and aliphatic polycarboxylic acids and amino acids. β-Aminocrotonic acid alkyl ester salt, 2-phenylindole or N, N' containing nitrogen-containing compounds
-Diphenylthiourea. Further, light stabilizers such as benzophenone, penntriazole, salicylate, substituted acrylonitrile, or hindered amine compounds can be used as appropriate depending on the purpose.

The chlorine-containing resins used in the present invention include polyvinyl chloride, hinyl chloride-hinyl acetate copolymer, hinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butadiene copolymer, and vinyl chloride-styrene copolymer. Coalescence, vinyl chloride-hynylidene chloride copolymer, vinyl chloride-
Urethane copolymers, chlorinated polyethylene, chlorinated polypropylene or their copolymers with vinyl chloride, vinyl chloride-styrene-maleic anhydride ternary copolymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene- Examples include blends of styrene copolymers, methacrylic acid ester-butadiene-styrene copolymers, etc. and polyvinyl chloride, block copolymers, graft copolymers, and the like.

The present invention can be applied to, for example, plasticizers, fillers, pigments, antistatic agents, antifogging agents, plate-out inhibitors, lubricants, flame retardants, anti-foaming agents, blowing agents, crosslinking agents, and other additives depending on the purpose of the molded product. A reinforcing agent or a processing aid can be used in combination.

The composition of the present invention is useful as a composition for low-toxicity or non-toxic plasticized soft or semi-hard molded articles among the general molded article applications of chlorine-containing resin compositions.

Next, in order to concretely explain the present invention, the invention will be disclosed in detail with reference to the following examples. However, the present invention is not limited to these examples in any way.

Example 1 In order to examine the thermal stabilization effect of a plasticized chlorine-containing resin composition to which stabilizers ① to 0 of the present invention were added, the following formulations were prepared:
Roll mill processing was performed at a temperature of 180°C for 5 minutes, resulting in a thickness of 0.
．． A uniform sheet with 5 solutions was created.

The colorability and transparency of this sheet by thermoforming were observed. Next, the sheet was tested by the method described below.

Test 1 A 20×40+= test piece was cut from the sheet and placed in a gear oven aging tester heated to a constant temperature for a certain period of time to conduct tests such as coloring due to thermal deterioration and time until black decomposition.

The results are shown in Table 1.

Test 2 A 50 x 80 test piece was cut from the sheet, 10 pieces were stacked together, and a press molding machine was used to mold the sample at 185°C at 100kg/
It was thermoformed for a certain period of time under the conditions of i, and tested for coloring and transparency due to thermal deterioration during pressing.

The results are shown in Table 1.

Compounded vinyl chloride resin 100 parts by weight* (Zeon 103EP) Dioctyl phthalate 40 I epoxidized soybean oil 2R barium stearate
0.5 #Barium nonyl phenate 0.51 Zinc stearate) 0.41 Triphenyl phosphite 0.6 Organic compounds (Table 1) 0.1” *Product from Ueon Japan Co., Ltd. Polymerization degree of approximately 1050 or less Margin examples 2 This example shows the thermal stabilization effect of a plasticized chlorine-containing resin composition prepared by adding an overbased barium dodecyl ferrate carbonate complex and 0 as a component of the stabilizer (c) of the present invention. In order to see the results, a sheet was prepared using the following formulation under the same conditions as in Example 1, and tested using the same test method as in Example 1 (Tests 1 and 2).

The results are shown in Table 2.

Compounded vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 40 L Epoxidized soybean oil 2 Overbased barium F decyl felt carbonate complex 0.8 I Barium stearate 0.2 Zinc stearate 0.4 Base Zinc 2-ethylhexoic acid 0.1# diphenylisodecyl phosphite
0.6I Organic Compounds (Table 2) Example 3 This example shows the following chlorine compound obtained by adding a white pigment (titanium oxide) and a filler (heavy calcium carbonate) to the stabilizer (A-0) of the present invention. A sheet was prepared from the containing resin composition under the same conditions as in Example 1, and tested using the same test methods (Tests 1 and 2) as in Example 1. The results are shown in Table 3.

Compounded vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 50 #Epoxidized soybean oil 2″ Titanium oxide (anatase type)
101 Heavy calcium carbonate 20 Barium stearate 0.5 Overbased barium nonyl felt carbonate complex 1.0 Zinc stearate 0.8 4.4-Impropyritine diphenyl alkyl (C12-C15) phosphorus Fight 0.61
Organic compounds (Table 3) 0.11
~ As is clear from the test results in Table 3, the stabilizer of the present invention, particularly the stabilizer formed by combining the organic compound of 0 represented by the general formula (1), that is, the specified dicarbonyl compound, and the compound of 8 with chlorine. When added to the containing resin, 8 is combined with other known cica7levonyl compounds such as 2-benzoylcyclohexanone, stearoyltetralone, 1,3-cyclohexanedione, stearoylbency7remethane or stearoylacetifremethane. When compared with other stabilizers, it can be seen that the heat stabilization, especially the effect of suppressing and preventing coloration in the early to middle stages, and the transparency are excellent. It also improves the processability of things like poor-a-door (
1 was also found to be superior to tehydroacetic acid (X).

Example 4 This example further improves the thermal stabilization performance of the chlorine-containing resin composition by adding other known stabilizing aids to the stabilizers (c) to (iii) of the present invention. A test was conducted for the purpose of In addition, the sheets were prepared and tested in the same manner as in Example 1 (Tests 1 and 2). The results are shown in Table 4.

Compounded vinyl chloride resin 100 parts by weight (Zeon 1
03EP) Barium stearate) 0.51'/-Rium nonyl fer-1-0,5 Overbased barium totesyl fert carboxylate complex 0.5 Zinc stearate 0.4 Zinc-p- tert-butylbenzony) 0.2#2-(2-
chlorobenzoyl)

Claims (1)

[Scope of Claims] A chlorine-containing resin containing at least one or more organometallic salt compounds of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or soot, and (c) the following general formula (formula A stabilized chlorine-containing resin composition characterized by adding at least one organic compound represented by the formula (wherein R represents an aryl group substituted with a halogen atom).