JPS58201851A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To prepare the titled resin composition having excellent thermal stability, especially excellent discoloration preventing property at the initial and intermediate periods, by compounding a base resin with an organic metal salt e.g. a salt of Ba, Ca, Mg, Sr, etc. and a ketoacetonitrile compound. CONSTITUTION:100pts.wt. of a chlorine-containing resin is compounded with (A) 0.01-10pts.wt., preferably 0.1-5pts.wt. of a low-toxic or non-toxic metallic soap selected from the organic metal salt of Ba, Ca, Mg, Sr, Li, K, Na, Zn and Sn and (B) 0.001-5pts.wt. preferably 0.01-3pts.wt. of the compound of formula [X is H, halogen, OH, alkyl, alkenyl, etc.; Y is H, alkyl, aryl, -CO-R (R is alkyl, aryl, etc.), etc.], e.g. benzoylacetonitrile. The organic group constituting the metallic soap of the component (A) is e.g. 6-22C mono- or dicarboxylic acid, 6-12C carbocyclic carboxylic acid, 4-10C heterocyclic carboxylic acid, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilized chlorine-containing resin composition characterized by adding a novel low-toxicity or non-toxic stabilizer to the chlorine-containing resin. More specifically, the present invention provides a stable method characterized by adding a low toxicity or non-toxic organometallic salt compound and a keto-aceto-nitrile compound represented by the general formula (1) below to a chlorine-containing resin. The present invention relates to a chlorine-containing resin composition.

Chlorine-containing resins are subjected to various thermoforming processes depending on their purpose of use, but dehydrochlorination is likely to occur due to the influence of heat during such thermoforming processes. This causes discoloration and/or physical deterioration, and further causes deterioration of the color tone and physical properties of the processed product, resulting in a significant decrease in commercial value. Therefore, various stabilizers have been proposed for the purpose of preventing discoloration and deterioration caused by such heat.

For example, (1) Cd-Ba, (2) Cd-Ba
-Pb, (3) Cd-Ba -Zn, (4)'Ba -
It is also well known that stabilizers in which organic layer phosphate esters, phenolic antioxidants, epoxy compounds, etc. are combined with metal soaps such as Zn, (5) Ca -Zn or (υ ~ (5)) have already been used. It is.

However, when a stabilizer containing the metal soaps mentioned in (1) to (3) above is added to the resin, it has an excellent effect of preventing discoloration and deterioration due to heat, etc., but such a stabilizer is Toxicity problems arise in hygiene and molded products. On the other hand, when stabilizers containing metal soaps (4) to (5) are added to the resin, there are relatively no problems in terms of hygiene and toxicity, but the thermal stability during thermoforming is insufficient. It is. Furthermore, various stabilizers have been researched and proposed for the purpose of supplementing this.

For example, in Japanese Patent Publication No. 42-8786, non-toxic (7)
A stabilizer consisting of a Ca-Zn metal soap or the like and a ketoacetic acid compound has been proposed, but there are problems in processability such as plate-out. In addition, the applicant has stated (4) to
((g)) The stabilizer consisting of a metal soap and a β-diketone compound is disclosed in Japanese Patent Publication No. 47948/1983,
It was disclosed in Japanese Patent Publication No. 30858 and Japanese Patent Publication No. 52-126452 (Japanese Patent Publication No. 57-9386). In addition, the above (4)
) to (5), each of which is a stabilizer comprising a metal soap and a metal complex salt of β-diketone, was disclosed in JP-A-53-9847.

However, it cannot be said that a stabilizer consisting of such a low-toxicity or non-toxic metal soap and a β-diketone compound or a metal complex salt thereof has been able to provide a stabilizing effect that is sufficiently satisfactory for practical purposes. In particular, it cannot be said that the technical problems in early to mid-term coloration prevention have been completely solved. Therefore, further improvements are desired by those skilled in the art.

As a result of various studies to solve these technical problems, the present inventors have discovered a chlorine-containing resin with excellent stability that satisfactorily satisfies initial discoloration prevention properties, mid-term discoloration prevention properties, and long-term discoloration prevention properties. Found the composition.

That is, in the present invention, based on 100 parts by weight of the chlorine-containing resin, (a) at least one or two or more organic metal salts selected from barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin; and (b) general formula [wherein X represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an alkoxy group, an acyloxy group, a mercapto group, an amino group (5) or an amide group, and Y is a hydrogen atom, an alkyl group,
A halogenated alkyl group, an aryl group, or an acyl group represented by -CO-R (where R is an alkyl group, a halogenated alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an aralkyl group, or a heterocyclic group). The keto-acetonitrile compound represented by
The present invention provides a stabilized chlorine-containing resin composition characterized by adding 1 to 5 parts by weight of O.

The organic metal salt (a) used in the present invention is generally called a metal soap, and the organic groups constituting the metal soap include monocarboxylic acids of saturated or unsaturated fatty acids having 6 to 22 carbon atoms; dicarboxylic acids, carbocyclic or heterocyclic carboxylic acids having 6 to 12 carbon atoms, M, hydroxy, alkoxy or oxocarboxylic acids having 2 to 10 carbon atoms, such as hexanoic acid, octanoic acid,
2-ethylhexylic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, (6) palmitic acid, stearic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid,
Riluic acid, linoleic acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, aladinic acid, erucic acid and animal fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, tall oil fatty acids and benzoic acid, toluyl. acid, chlorobenzoic acid, p-t-
Butylbenzoic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
Methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, hydroatrobic acid, fulic acid, thenic acid,
Nicotinic acid, isonicotinic acid, glycolic acid, glyceric acid, lactic acid, malic acid, tartaric acid, citric acid, acetoacetic acid, levulinic acid, salicylic acid, anisic acid, cyclohexanoic acid, or a mixed acid of these carboxylic acids. Furthermore, as other organic groups, phenols or alkylphenols having 6 to 24 carbon atoms are also useful, such as evaphenol, pyrocatechol, hydroquinone, pyrocatechol, Kunsol, p-
Mention may be made of t-butylphenol, p-octylphenol, nonylphenol or dinonylphenol organic residues. Further, the tin compound may be typified by an alkyltin compound. For example, monomethyltin laurate, dimethyltin laurate, dibutyltin laurate, dioctyltin laurate,
Dibutyltin maleate polymer, dibutyltin maleate alkyl ester salt, dioctyltin maleate polymer, dioctyltin maleate alkyl ester salt, monomethyltin thioglycolic acid alkyl ester salt, dimethyltin thioglycolic acid alkyl ester salt,
These include dimethyltin thiopropionate, dibutyltin thioglycolic acid alkyl ester salt, dibutyltin thiopropionate, monooctyltin thiogelcholic acid alkyl ester salt, dioctyltin thioglycolic acid alkyl ester salt, dioctyltin propionate, and the like. The organometallic salt compound bonded to these organic groups may be an acid salt or a neutral salt, or may be a basic salt bonded to equimolar or more of the metal. When used in the present invention, such 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. It's okay. In this case, the ratio of zinc salt to other metal salt is usually 1.0:0.1 to 10 by weight, preferably 1.0.
20, 2-5.0. Further, the organic metal salt compound is added in an amount of 0.01 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 keto-aceto-nitrile compound represented by the general formula (I) @) used in the present invention include benzoylacetonitrile, methylbenzoylacetonitrile, octylbenzoylacetonitrile, allylbenzoylacetonitrile, trifluoromethylbenzoylacetonitrile, 2-chloroethyl-benzoylacetonitrile, 2-hydroxyethyl-benzoylacetonitrile, phenylbenzoylacetonitrile, benzylhenzoylacetonitrile, cinnamylpenzoylacetonitrile, phenacylbenzoylacetonitrile, 4-pp benzoylacetonitrile, acetylbenzoylacetonitrile, octoylbenzoylacetonitrile , stearoyl acetonitrile, 2-acroylbenzoylacetonitrile, 4-chloro-acetylbenzoylacetonitrile, acetylanisoylacetonitrile, acetoacetyl-benzoylacetonitrile, malonylbis(benzoylacetonitrile), fumaroylbis(benzoylacetonitrile), chloroacetylbenzoylacetonitrile, trifluoroacetyl Benzoylacetonitrile, trifluoroacetoacetyl (10) Rubenzoylacetonitrile, thiodipropionyl bis(benzoylacetonitrile), dibenzoylacetonitrile, p-benzoylacetylbenzoyl-penzoylacetonitrile, terephthaloyl bis(pensoy,
(benzoylacetonitrile), phthaloylbis(benzoylacetonitrile), phenylacetylbenzoylacetonitrile, benzoylacetyl-benzoylacetonitrile, cinnamoylbenzoylacetonitrile, cyclopentanecarbonylbenzoylacetonitrile, leclohexane-luponylpenzoylacetonitrile, 1-cyclohexene-luponylpenzoylacetonitrile , 2-
Examples include tenoylpenzoylacetonitrile, 2-furoylbenzoylacetonitrile, nicotinoylbenzoylacetonitrile, and the like. The above (b)
The buto-acetonitrile compound of chlorine-containing resin 100
1 to 5 parts by weight of O,OO, preferably 0.00 parts by weight.
01 to 3 parts by weight are added. However, the above (a) to (
The stabilizer having (b) as an essential component is one that is added to a chlorine-containing resin to exhibit excellent thermal stability, especially early to mid-term coloration prevention.

In the present invention, in addition to the two components (a) to (b), the thermal stabilization performance and processability are further improved by using a known stabilizer or stabilizing aid. .

Such useful stabilizers or stabilizing aids include phosphites such as trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, trialkyl phosphites, bisphenol phosphites, polyhydric alcohol phosphites, and also alkyl, Acidic phosphites in which one or two organic residues such as aryl or aralkyl are replaced by hydrogen atoms, such as triisooctylphosphite, triisodecylphosphite, tridecylphosphite, diisodecylmonophenylphosphite , tribenzyl phosphite,
Trinonylphenyl phosphite.

Hydrogenated 4,4'-isopropylidene diphenyl phosphite, 4,4'-isopropylidene diphenyl alkyl phosphite, diphenyl acid phosphite,
These include diisodecyl acid phosphite and dibenzyl acid phosphite. In addition, phenolic compounds such as i, t, alkylated phenol, alkylated phenol nystyl, alkylated phenol ether, alkylene or alkylidene bisphenol, polyalkylated phenol or thiohistalkylated phenol are representative compounds. Examples include butylated hydroxytoluene or 4°4'-thiobis(6-t-butyl-m-cresol), and thiodipropionic acid alkyl ester. Also, inorganic metal salt compounds, such as hydroxides, oxides or carbonates of metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, strontium, zinc, aluminum, indium, zirconium and tin. Furthermore, (13) is a basic inorganic salt, such as phosphoric acid, phosphorous acid, silicic acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, or boric acid and the above metal or a chloride, oxide, or water of the metal. It is an oxide or a mixture of these.

Examples of the epoxy compound include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. Other stabilizers or stabilizing aids such as pentaerythritol, dipentaerythritol, mannitol or sorbitol, as well as ester compounds of the polyol and fatty acids. Nitrogen-containing compounds such as β-aminocrotonic acid alkyl ester salt, 2-phenylindole or N
, N'-diphenylthiourea. Light stabilizers such as benzophenone, benzotriazole, salicylate or substituted acrylonitrile compounds are useful.

In the present invention, chlorine-containing resins include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-pro(14)pyrene copolymer, vinyl chloride-butadiene copolymer, chloride Vinyl-styrene copolymer, vinyl chloride-vinylidene chloride copolymer, chlorinated polyethylene, chlorinated polypropylene or a copolymer of these with vinyl chloride, vinyl chloride-styrene-maleic anhydride terpolymer, and even Ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer sudo blend product with polyvinyl chloride, block copolymer or graft copolymer, etc. can be mentioned.

In the present invention, depending on the purpose of the molded product, for example, plasticizers, fillers, pigments, antistatic agents, antifogging agents, antiplate-out agents, lubricants, flame retardants, antifungal agents, blowing agents, crosslinking agents, etc. A reinforcing agent or a processing aid may be used in combination.

The composition of the present invention is useful as a low-toxicity hard or semi-hard composition among the general molded articles of chlorine-containing resin compositions.

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

Examples 1 to 3 and Comparative Example 1 In order to examine the thermal stabilization effect of chlorine-containing resin compositions to which stabilizers (a) to (b) of the present invention were added, the following formulations were prepared.
Roll milling was performed at a temperature of 180°C for 5 minutes to a thickness of 0.
A uniform sheet of 5 wn was prepared.

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

Test 1 Cut a 20×40so+ test piece from the sheet,
The material was placed in a gear open aging tester heated to a certain 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 A 50 x 80-sized test piece was cut out from the sheet, 10 pieces were stacked, and a press molding machine was used to mold the sample at 185°C and 100 kg/
- It was molded for a certain period of time under the conditions of - and tested for coloring and transparency due to thermal deterioration during pressing. The results are also listed in Table 1.

<Composition> 100 parts by weight of vinyl chloride resin (Zeon 1
03EP-8)* Epoxidized soybean oil 31 Barium stearate 0.81 Barium nonylphenol) 0.8 & Zinc stearate) 0.41 Keto-aceto-nitrile compound (Table 1) Chestnut Nippon Zeon product Below margin (17 ) Reprint of the specification (no change in content) (18) In Examples 4 to 16 and Comparative Examples 2 to 2, plasticizing chlorine containing stabilizers (a) to (b)) of the present invention were added. In order to examine the stabilizing effect of the resin composition, a sheet was prepared using the following formulation under the same conditions as in Example 1, and the test was conducted using the same test method as in Example 1 (Tests 1 and 2). are as shown in Tables 2 and 3.

<Blend> Vinyl chloride resin (Zeon 103 100 parts by weight EP) Dioctyl phthalate 48 l Epoxidized soybean oil 21 Barium stearate
O14 Zinc Stearate 0.
4 diphenylisodecylphos 0.5 phite
' Keto-aceto-nitrile compounds (Table 2.3) Other stabilizers (Table 3) Examples 17 to 22 and Comparative Example 7 In this example, the present invention (a) to (→ and white pigment (oxidized A sheet of the following chlorine-containing resin composition containing titanium (titanium) and a filler (heavy calcium carbonate) was prepared under the same conditions as in Example 1, and the same test methods as in Example 1 (Test 1 and 2, except for transparency).The results are shown in Tables 4 and 5.

Mixture> 100 parts by weight of vinyl chloride resin (Zeon 1
03EP) Dioctyl phthalate 48-Epoxidized soybean oil Titanium oxide 21 (anatase type)
10 I calcium carbonate 20 −
Zinc stearate 0.81 Barium stearate 0.81 Barium nonylfer) 0.81 Diphenylisodecyl phosphite 0.51 Keto-aceto-nitrile compound (Table 4)
(22) (21) Procedural amendment (method) September 76, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office ■, Indication of the case 1982 Patent application No. 82441, Title of invention Stabilized chlorine-containing resin composition 3. Quantitative relationship with the case of the person making the amendment Patent applicant address: 1-10-1, Nihonbashi Honmachi, Chuo-ku, Tokyo 103 4. Date of amendment order: August 31, 1980 (shipment date) 5. Amendment Column of the table of the subject specification (23) 6. Table of the specification of the contents of the amendment, Table 1 (page 18), Table 2 (page 20)
, Table 3 (page 21), and Table 4 (page 23) as attached (2)

Claims (1)

[Claims] Based on 100 parts by weight of the chlorine-containing resin, as a stabilizer, (a) at least one selected from barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or an organic metal salt of tin; (b) General formula [wherein X represents a hydrogen atom, halogen atom, hydroxy group, alkyl group, alkenyl group, alkoxy group, acyloxy group, mercapto group, amino group or amide group, and Y represents hydrogen] atom, alkyl group,) 10genated alkyl group,
Aryl group or acyl group represented by -CO-R (
However, R represents an alkyl group, a hagenated alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an aralkyl group, or a heterocyclic group]
1 to 5 parts by weight of a stabilized chlorine-containing resin composition.