JPH0158214B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a stabilized chlorine-containing resin characterized by adding a low toxicity or non-toxic organic metal salt compound and an organic compound represented by the general formula () below to a chlorine-containing resin. The present invention relates to a 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. It is well known that this causes a deterioration in the color tone or physical properties of the molded product, 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, organometallic salt compounds of (1) cadmium-barium, (2) cadmium-barium-lead, (3) cadmium-barium-zinc, (4) barium-zinc, or (5) calcium-zinc, Stabilizers in combination with stabilizing aids such as phosphoric acid esters, phenolic antioxidants or epoxy compounds are commonly used. However, when a stabilizer consisting of a combination of the organic metal salts (1) to (3) and the stabilizing aid described above 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 hygiene 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 to improve this problem. For example, in Japanese Patent Publication No. 42-8786, the above (5)
A stabilizer consisting of a Ca-Zn organic metal salt and a ketoacetic acid compound has been proposed, but there are problems with processability such as plate-out. In addition, (4) above
A stabilizer consisting of the organometallic salt of ~(5) and a β-diketone compound was discovered as disclosed in Japanese Patent Publication No. 52-47948, Japanese Patent Publication No. 57-9386, etc., and such a stabilizing method was proposed. did. Furthermore, the above (4)~
A stabilizer consisting of the organic metal salt (5) and a metal complex salt of a β-diketone compound was discovered as disclosed in Japanese Patent Publication No. 57-39260, and each was proposed.
However, when a stabilizer consisting of a combination of such a low-toxic or non-toxic organic metal salt, a β-diketone compound or a metal complex salt thereof, and a stabilizing aid is used, it is fully satisfactory in industrial practice. It cannot be said that a thermal stabilizing effect could be obtained. 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. Therefore, improvement in thermal stability is strongly desired. 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 that sufficiently suppresses discoloration in the early to middle stages, and has completed the present invention. It is something that That is, the present invention provides a chlorine-containing resin containing (A) at least one or two or more organometallic salt compounds of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin, and (B) the following general formula: (wherein R represents an aryl group substituted with a halogen atom), and at least one of the specified dicarbonyl compounds which is an organic compound represented by: It is a composition. The organic metal salt compound of the component (A) 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, carbocyclic acids having 6 to 16 carbon atoms, or carbocyclic acids having 2 to 16 carbon atoms.
hydroxy, alkoxy, oxocarboxylic acids 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, palmitic acid, stearic acid. acids, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid,
Linoleic acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, aladinic acid, erucic acid and benzoic acid, toluic acid, chlorobenzoic acid, p-tert-butylbenzoic acid, xylic acid, ethylbenzoic acid, p- octylbenzoic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azeic acid, sebacic acid, methacrylic acid, crotonic acid, isocrotonic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid,
Cinnamic acid, hydroatropic acid, glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, acetoacetic acid, levulinic acid, salicylic acid, anisic acid, cyclohexanoic acid, furic acid, thenic acid, nicotinic acid, isonicotinic acid or A mixed acid of these carboxylic acids. Further examples include alanine, methionine, aspartic acid, and glutamic acid. In addition, other organic residues include carbon atoms of 6 to 24
Also useful are phenols such as phenol, pyrocatechol, resorcinol, pyrogallol, cresol, p-tert-butylphenol,
Examples include xylenol, p-octylphenol, nonylphenol, dinonylphenol, decylphenol, and dodecylphenol. Examples of tin compounds include alkyltin compounds, such as dimethyltin laurate, dibutyltin laurate, dioctyltin laurate, dibutyltin maleate polymer, dibutyltin maleate alkyl ester salt, and dioctyltin maleate alkyl ester. salt, dimethyltinthioglycolic acid alkyl ester salt, dimethyltinthiopropionate, dibutyltinthioglycolic acid alkyl ester salt,
Examples include dibutyltinthiopropionate, dioctyltinthioglycolic acid alkyl ester salt, and dioctyltinthiopropionate. Thus, the organometallic salt compound bound to such an organic residue may be an acidic salt or a neutral salt;
It may be a basic or overbased salt in which metals are bound in equal moles or more. When used in the present invention, these organometallic salt compounds may be used alone or in combination with zinc salts and other metal salts such as barium, calcium, magnesium, strontium, lithium, potassium, sodium or tin metal salts. is more preferable. In this case, the ratio of zinc salt to other metal salt is usually in a weight ratio of 1.0:0.1 to 10, preferably 1.0:0.2 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. Examples of the organic compound represented by the general formula () (i.e., dicarbonyl compound) of the component (B) of the stabilizer used in the present invention include 2-(2-chlorobenzoyl)cyclohexanone, 2-(3-chlorobenzoyl)cyclohexanone, 2-(4-chlorobenzoyl)cyclohexanone, 2-(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 -fluorobenzoyl)cyclohexanone, 2-pentafluorobenzoylcyclohexanone, etc. The above dicarbonyl compound (B) is added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the chlorine-containing resin. Accordingly, the present invention provides a stabilized resin composition obtained by adding a stabilizer having the two components (A) to (B) as essential constituents to a chlorine-containing resin, Excellent thermal stability, especially suppressing and preventing early to mid-term discoloration. In addition to the two components (A) to (B), the resin composition of the present invention can improve thermal stabilization performance, processability, weather resistance, etc. by adding a known stabilizer or stabilizing aid. will be further improved. Such useful stabilizers or stabilizing aids include organic phosphites such as trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, triallaralkyl phosphites,
Examples include bisphenol A phosphite and polyhydric alcohol phosphite. Typical compounds include triisooctyl phosphite,
Triisodecyl phosphite, triphenyl phosphite, diisodecyl monophenyl phosphite, diphenyl monodecyl phosphite, tribenzyl phosphite, trinonylphenyl phosphite, 4,4'-isopropylidene diphenyl alkyl (C ₁₂ - _C15 ) Phosphite, poly(dipropylene glycol) phenyl phosphite, distearyl pentaerythritol diphosphite,
These include tris(4-oxy-3,5-di-tert-butylphenyl) phosphite and heptakis(dipropylene glycol) triphosphite. In addition, the above organic phosphite ester,
Acid phosphites in which one or two of the organic residues such as alkyl, aryl or aralkyl are replaced by hydrogen atoms, such as diphenyl acid phosphite, diisodecyl acid phosphite, isodecylphenyl acid These include phosphite, dibenzyl acid phosphite, monophenyl acid phosphite, monotridecyl acid phosphite, monononylphenyl acid phosphite, and the like. Also, phosphate compounds such as diisooctyl phosphate,
Ditridecyl phosphate, dilauryl phosphate, distearyl phosphate, diphenyl phosphate, phenyl isodecyl phosphate,
Examples include organic phosphorus compounds such as dibenzole phosphate and dinonylphenyl phosphate. Examples of phenolic compounds include alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenols, thiobisalkylated phenols, and typical compounds include butylated hydroxytoluene, butylated hydroxy Anisole, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-m-cresol), and other thiodipropionic acid alkyl esters. It is an antioxidant such as. Also, inorganic metal salt compounds, such as hydroxides of metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, strontium, zinc, aluminum, indium and tin;
oxides or carbonates, and basic inorganic salts such as phosphoric acid, phosphorous acid, silicic acid, nitric acid,
Nitrous acid, sulfuric acid, sulfite or boric acid and the above metals or chlorides, oxides, hydroxides or mixtures or double salts thereof, such as calcium oxide, aluminum oxide, magnesium oxide, calcium hydroxide, Magnesium hydroxide, aluminum hydroxide, zinc borate, sodium silicate, magnesium silicate, aluminum sulfate, basic aluminum sulfate, potassium aluminum sulfate, sodium phosphate, magnesium phosphate, magnesium perchlorate, barium perchlorate, These include sodium perchlorate, synthetic hydrotalcite, and synthetic zeolite based on aluminosilicate. Commonly used stabilizing aids as described below can be added to the resin composition of the present invention. For example, epoxy compounds include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. Also, polyhydric alcohol compounds such as pentaerythritol, dipentythritol, mannitol, sorbitol, or ester compounds of these polyhydric alcohols and aliphatic polyhydric carboxylic acids and amino acids. β-Aminocrotonic acid alkyl ester salt, 2-phenylindole or N,N'-diphenylthiourea which is a nitrogen-containing compound. Also,
Light stabilizers such as benzophenone, benzotriazole, salicylate, substituted acrylonitrile, or hindered amine compounds can be used as appropriate depending on the purpose. In the present invention, chlorine-containing resins include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene copolymer, etc. Polymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-urethane copolymers, chlorinated polyethylene, chlorinated polypropylene or copolymers of these with vinyl chloride, vinyl chloride-styrene-maleic anhydride ternary copolymers Blends, block copolymers or graft copolymers of polyvinyl chloride and ethylene-vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers, methacrylate ester-butadiene-styrene copolymers, etc. etc. can be given. The present invention can be applied to, for example, plasticizers, fillers, pigments, antistatic agents, antifogging agents, antiplate-out agents, lubricants, flame retardants, antifungal 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 plasticized soft or semi-hard molded articles with low toxicity or non-toxicity even after the use of general chlorine-containing resin compositions as molded articles. Next, in order to concretely explain the present invention, the invention will be disclosed in detail using the following examples. However, the present invention is not limited to these Examples. Example 1 In order to examine the thermal stabilization effect of the plasticized chlorine-containing resin composition to which the stabilizers (A) to (B) of the present invention were added,
The following formulation was roll milled at a temperature of 180° C. for 5 minutes to produce a uniform sheet with a thickness of 0.5 mm. The colorability and transparency of this sheet by thermoforming were observed. Next, the sheet was tested by the method described below. Test 1 Cut a 20 x 40 mm test piece from the sheet,
The specimens were placed in a gear oven aging tester heated to a constant temperature for a certain period of time, and tests were conducted to determine coloration due to thermal deterioration and the time until black decomposition. The results are shown in Table 1. Test 2 Cut a 50 x 80 mm test piece from the sheet,
Stack 10 sheets of this and use a press molding machine at 185℃ - 100Kg/
It was thermoformed for a certain period of time under conditions of cm ² and tested for coloration and transparency due to thermal deterioration during pressing. The results are shown in Table 1. Compound Vinyl chloride resin* (Zeon 103EP) 100 parts by weight Dioctyl phthalate 40 Epoxidized soybean oil 2 Barium stearate 0.5 Barium nonyl phenate 0.5 Zinc stearate 0.4 Triphenyl phosphite 0.6 Organic compound (1st Table) 0.1 *Nippon Zeon product Polymerization degree approximately 1050

[Table] Example 2 This example shows that the stabilizers (A) to (B) of the present invention, especially (A)
In order to examine the thermal stabilization effect of a plasticized chlorine-containing resin composition prepared by adding an overbased barium dodecyl phenolate carbonate complex and (B) as components, the following formulation was subjected to the same conditions as in Example 1. A sheet was created using the same test method as in Example 1 (Test 1).
and 2). The results are shown in Table 2. Blend Vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 40 Epoxidized soybean oil 2 Overbased barium dodecyl phenolate carbonate complex 0.8 Barium stearate 0.2 Zinc stearate 0.4 Basic zinc 2-ethylhexoic acid 0.1 〃 Diphenylisodecyl phosphite 0.6 〃 Organic compounds (Table 2)

[Table] Example 3 In this example, white pigment (titanium oxide) and filler (ground calcium carbonate) were added to the stabilizers (A) to (B) of the present invention.
A sheet of the following chlorine-containing resin composition containing the following was prepared 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 3. Compound Vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 2 Tin oxide (anatase type) 10 Heavy calcium carbonate 20 Barium stearate 0.5 Overbased barium nonyl phenolate carbonate Complex 1.0 〃 Zinc stearate 0.8 〃 4,4-isopropylidene diphenylalkyl (C ₁₂ - C ₁₅ ) phosphite 0.6 〃 Organic compound (Table 3) 0.1 〃

[Table] As is clear from the test results in Tables 1 to 3 above, the stabilizer of the present invention, particularly the organic compound (B) represented by the general formula (), that is, the specified dicarbonyl compound, and (A ) is added to the chlorine-containing resin, other known dicarbonyl compounds such as 2-benzoylcyclohexanone,
A comparison of a stabilizer made by combining stearoyltetralone, 1,3-cyclohexanedione, stearoylbenzoylmethane, or stearoyl acetylmethane with (A) shows that thermal stabilization, especially suppression of coloration in the early to middle stages, and It can be seen that the prevention effect and furthermore the transparency is excellent. It was also found to be superior to dehydroacetic acid in terms of processability such as plate-out. Example 4 This example demonstrates the performance of thermal stabilization of the chlorine-containing resin composition by further adding other known stabilizing aids to the stabilizers (A) to (B) of the present invention. The test was conducted with the aim of further improving the performance. 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. Compound vinyl chloride resin (Zeon 103EP) 100 parts by weight Barium stearate 0.5 〃 Barium nonyl phenolate 0.5 〃 Overbased barium dodecyl phenolate carbonate complex 0.5 〃 Zinc stearate 0.4 〃 Zinc-p-tert-butyl benzoate 0.2 〃 2 -(2-chlorobenzoyl)cyclohexanone 0.1 Stabilizing aids and other additives (Table 4)

【table】

Claims (1)

[Scope of Claims] 1. A chlorine-containing resin containing (A) at least one or more organic metal salt compounds of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc or tin, and (B) the following general compounds: formula (In the formula, R represents an aryl group substituted with a halogen atom.) A stabilized chlorine-containing resin composition characterized by adding at least one organic compound represented by the following.