JPS59217746A - Stabilized chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by adding a specific metal salt of organic acid and a specific dicarbonyl compound, thus showing excellent thermal stability with prevention of discoloration at initial to medium stages with the passage of time under heating without problems of toxicity as well. CONSTITUTION:A chlorine-containing resin is combined with (A) an organic acid salt of barium, calcium, sodium, magnesium, strontium, lithium, potassium zinc or tin and (B) a metal complex of a dicarbonium compound of the formula (M is an atom of group I a, IIa, IIb, IIIb, IVa, IVb, Vb or alkylated tin; X is H, halogen, hydroxy, alkyl, alkoxy, acyl; n<1>, n<2> are 1-5). The metal salt of organic acid is preferably a combination of its zinc salt and another metal salt at a weight ratio of 1/(0.1-10). It is preferred that 100pts.wt. of the resin are com bined with 0.1-5pts.wt. of component A and 0.01-1pt.wt. of component B.

Description

Detailed Description of the Invention The present invention is made by adding a low toxicity or non-toxic organic acid metal salt and a metal complex salt of a dicarbonyl compound represented by the general formula (1) below to a chlorine-containing resin. The present invention relates to a stabilized chlorine-containing resin composition. 1
Polychlorine-containing resins are subjected to various thermoforming processes9 depending on their purpose of use, but during such thermoforming processes, thermal decomposition due to dehydrochlorination is likely to occur 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, organic acid metal salts of (1) cadmium-barium, c2) cadmium-barium-lead, (3) cadmium-barium-zinc, (4) barium-zinc or calcium-zinc, and organic surface phosphorus. It is known that stabilizers are used in combination with stabilizing aids such as acid esters, phenolic antioxidants, or epoxy compounds. When using a stabilizer consisting of a combination of and the above-mentioned stabilizing aid,
Although almost satisfactory effects have been obtained in terms of thermal stability, there are drawbacks such as problems in working environment hygiene and toxicity in molded products. On the other hand, a low-toxic or non-toxic stable compound comprising a combination of an organic acid metal salt of group (4) to (group), the above-mentioned stabilizing aid, and further a carboxylic acid ester of aminocrotonic acid ester and dipentaerythritol, etc. When using this agent, there are relatively no problems in terms of hygiene and toxicity, but the thermal stability during thermoforming processing, especially the prevention of early to mid-term discoloration over heat aging, is insufficient.Therefore, the purpose of improving this is Various stabilizers have been studied, proposed, and put into practical use.

For example, Japanese Patent Publication No. 42-8786 proposes a stabilizer consisting of the organic acid metal salt (9) and dehydroacetic acid, but there are problems in processability such as plate-out. (4) to (9) organic acid metal salt and β
- A stabilizer consisting of a diketone compound
The invention was discovered and proposed as disclosed in Publication No. 7948 and Publication No. 57-9386. Furthermore, the above (4) to (5)
an organic acid metal salt of and a metal complex salt of a β-diketone compound;
As disclosed in Japanese Patent Publication No. 57-39260, stabilizers consisting of the following were discovered and proposed. In addition, Japanese Patent Application No. 57-196772 discloses a stabilizer consisting of a dicarbonyl compound characterized by having one keto group on an alicyclic group and the organic acid metal salts listed in (4) to (2) above. and same 57
As is clear from No.-222951, the present inventors previously invented and filed a patent application.

However, when a stabilizer consisting of a combination of such a low-toxicity or non-toxic organic acid metal salt, a β-diketone compound or its metal complex salt, and a stabilizing agent is used, it is fully satisfactory in industrial practice. It cannot be said that the desired thermal stabilizing effect was achieved. For example, when a resin composition prepared by blending a large amount of filler or white pigment into the resin is thermoformed, the thermal stabilization, especially the effect of preventing discoloration in the early to middle stages, is not sufficient.

Therefore, further improvement is desired.

As a result of various studies to solve these technical problems, the present inventors have developed a chlorine-containing resin composition that has an excellent thermal stabilizing effect, especially an excellent effect on preventing discoloration in the early to middle stages of heat aging. The heading completes the invention.

That is, in the present invention, (a) barium,
At least one (5) or two or more organic acid metal salts of calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin, and (b) the following general formula (where M is a member of the periodic table of elements) Ta group, 11a and nth group
Group b, Group 1b, Wa, Group 1Vb, Group Vb, or alkylated tin, X represents a hydrogen atom, a halogen atom, hydroxy, an alkoxy group, and each of nl and n2 represents an integer of 1 to 5. . ) A stabilized chlorine-containing resin composition is provided by adding a metal complex salt of a dicarbonyl compound represented by:

The stabilizer for the chlorine-containing resin in the present invention, that is, the organic acid metal salt of the constituent component (→) is generally called metal soap, and the organic acid residues constituting the metal soap include the following carboxylic acid and phenolic 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 C2-C16 hydroxy, alkoxy, oxo- 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, valmitic acid, stearic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, liruric acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, Aladdin acids, erucic acid and benzoic acid, toluic acid, chrobenzoic acid, P,-tert-butylbenzoic acid, xylic acid, ethylbenzoic acid, P-octylbenzoic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
Methacrylic 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 a mixed acid of these carboxylic acids. Further examples include alanine, methionine, aspartic acid, and glutamic acid.

Phenols having 6 to 24 carbon atoms are also useful, such as phenol, pyrocaffyl, resoricinol, pyrogallol, cresol, P-E7'thylphenol, xylenol, P-octylphenol, nonylphenol, dinonylphenol, tesylphenol. , dodecylphenol, etc.

In addition, tin compounds are typified by alkyltin compounds, such as dimethyltin laurate, dibutyltin laurate, dioctyltin laurate, dibutyltin maleate polymer, dibutyltin maleate alkyl ester salt, dioctyltin maleate alkyl ester salt, Examples include dimethyltin thioglycolic acid alkyl ester salt, dimethyltin thiopropionate, dibutyltin thioglycolic acid alkyl ester salt, dibutyltin thiopropionate, dioctyltin thioglycolic acid alkyl ester salt, or dioctyltin thiopropionate. can.

Thus, the organic acid metal salt bound to such organic acid residues may be an acidic salt or a neutral salt, and a basic salt or an overbased salt in which more than the total chemical equivalents of the metal in the salt are bound. It may also be salt. When used in the present invention, these organic acid metal salts 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. Group (9) Combination is more preferable. In this case, the ratio with zinc salt is usually 1.
0: weight ratio of 0.1 to 10, preferably 1.0:
It is 0.2 to 5.0. The organic acid metal salt 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.

The metals constituting the metal complex salt of the dicarbonyl compound represented by the general formula (1) (c) used in the present invention include Groups Ⅰ, A, 11a and NB of the Periodic Table of the Elements,
Group Wb, Group 1 Va and Group 1 Vb, Group Vb or alkylated tin compounds.

Therefore, examples of the dicarbonyl compound represented by the general formula (1) include 2-benzoylcyclopentanone,
2-(2- or 3- or 4-μlobenzoyl)cyclopentanone, 2-(2,4- or 2,5-
or 2,6- or cyclopentanone, 2-(2-fluorobenzoyl)cyclopentanone, 2-( 2-(10) or 3- or 4-methylbenzoyl)cyclopentanone, 2-(2-4L<3-or 4-methoxybenzoyl)cyclopentanone, 2-(4-methylsalicypylcyclo Pentanone, 2-(4-chloro-2-
methoxybenzoyl)cyclopentanone or 2-(5
-chlorosalicyloyl) cyclopentanone and other dicarbonyl compounds. Next, representative formulas of metal complex salts of dicarbonyl compounds are shown in Table 1 below.

1st Table 41~(1) M=Zn' (2) Bal~(3) Ca' (4) Na' (5) Sn (C4He)2
A 2~(1) M= Zn' (2) Ba' (3) Ca #(4)Na' (5) Sb' (6) Sn' (7) Sn (C4H9)2I 43~(1) M= Zn l(2) Ba I(3) Ca (13) 44~(1) M=Zn z (2) Bal (3) Na A 5~(1) M= Zn' (2) Ba' (3) Examples include Sn (C4H9)2. The metal complex salt of the dicarbonyl compound (c) above is used in an amount of o, o o i to 3 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.
1 part by weight is added.

Therefore, the present invention provides a stabilized resin composition obtained by adding a stabilizer having the above two components (→ to (c)) to a chlorine (14)-containing resin. Therefore, it has excellent thermal stability, especially suppressing and preventing discoloration in the early to middle stages.

In addition to the above two components (a) to (c), the resin composition of the present invention can improve heat stabilization performance, processability, and weather resistance by adding a known stabilizer or stabilizing aid. This will further improve performance, etc.

Such useful stabilizers or stabilizing aids include organic phosphites such as trialkyl phosphites, triarylphosphites, alkylaryl phosphites,
Examples include trialkyl phosphite, bisphenol A phosphite, and polyhydric alcohol phosphite. Typical compounds include triisooctyl phosphite, triisodecyl phosphite, triphenyl phosphite, diisodecylmonophenyl phosphite, diphenyl monodecyl phosphite, tribenzyl phosphite, trinonylphenyl phosphite, 4.4
'-isopropylidene diphenylalkyl (C12-C
ts) Phosphite, poly(dipropylene glycol)
These include phenyl phosphite, distearyl pentaerythritol diphosphite, tris (4-oxy-3,5-di-tert-butylphenyl) phosphite, heptakis (dipropylene glycol) triphosphite, and the like.

In addition, acid phosphites in which one or two of the organic residues such as atte, alkyl, aryl, or aralkyl are substituted with hydrogen atoms in the above-mentioned organic phosphites, such as diphenyl acid phosphite, diisodecyl acid phosphite, These include isodecyl phenyl acid phosphite, dibenzyl acid phosphite, monophenyl acid phosphite, monotridecyl acid phosphite, and heptanonylphenyl acid phosphite.

In addition, phosphonate compounds such as diisooctylphosphonate, ditridecylphosphonate, dilaurylphosphonate, distearylphosphonate *-), diphenylphosphonate, phenylisodecylphosphonate, dibenzylphosphonate, dinonylphenylphosphonate, triphenylphosphonate, diphenylisodecyl These are organic phosphorus compounds such as phosphonate, tribenzylphosphonate, and trinonylphenylphosphonate.

Examples of phenolic compounds include alkylated phenol, alkylated phenol ester, alkylene or alkylidene bisphenol, polyalkylated phenol, thiobisalkylated phenol, and representative 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 piperidine compounds such as 2,2,6,6-
Antioxidants such as tetramethylpiperidin-4-ol ester and thiodipropionic acid alkyl ester.

Also, inorganic metal salt compounds such as lithium, (17) hydroxides of metals selected from the group consisting of sodium, potassium, magnesium, calcium, barium, strontium, zinc, aluminum, indium and tin;
oxides or carbonates, as well as basic inorganic salts,
Examples include phosphoric acid, phosphorous acid, □silicic acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, or boric acid and the above-mentioned metal or a chloride, oxide, or hydroxide of the above-mentioned metal, or a mixture thereof.

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, dipentaerythritol, mannitol, sorbitol, or ester compounds of these polyhydric alcohols and aliphatic polycarboxylic acids and amino acids. β-aminocrotonic acid alkyl ester salt, 2- which is a nitrogen-containing compound (18)
Phenyl indole! or N,N-diphenylthiourea. Further, 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. Polymer, vinyl chloride-vinylidene 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, 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 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 the plasticized chlorine-containing resin composition to which the stabilizer (ω~(c)) of the present invention was added, the following formulation was roll milled at a temperature of 180°C for 5 minutes. and
A uniform sheet with a thickness of 0.51 m was prepared.

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

Test 1 A 20 x 40 mm test piece was cut from the sheet and placed in a gear open aging tester heated to a certain temperature for a certain period of time to conduct tests such as coloration due to thermal deterioration and time until black decomposition.

Test 2 A 50 x 80 m test piece was cut from the sheet, 10 pieces were stacked, and a press molding machine was used to heat the test piece at 185°C and 100Kf/
It was thermoformed for a certain period of time under conditions of cII, and a coloring test was conducted due to thermal deterioration during pressing.

(21) Compounded vinyl chloride resin 100 parts by weight* (Zeon 103EP) Dioctyl phthalate 3ol Epoxidized soybean oil 21 Anatase type titanium oxide 15 N heavy calcium carbonate
3o l barium stearate 0.
81 overbased barium nonylphene/0.8 rutocarbonate complex zinc stearate 0.31 zinc 2-
Ethylhexoether) 0.31 Triphenyl phosphite 0.61 Metal complex salt of dicarbonyl compound 0.11 *Manufactured by Nippon Zeon, average degree of polymerization 1
050 (22) As is clear from the test results in Table 2 above, the stabilizer of the present invention, particularly the compound represented by general formula (1), that is, the metal complex salt of the specified dicarbonyl compound, and ( a
) When a stabilizer consisting of an organic acid metal salt of Ah, Ruiha 2
It can be seen that -benzoylcyclopentanone is superior in heat stabilization, particularly in the early to middle stage discoloration suppressing and preventing effects, compared to zinc acetylacetone or barium benzoylacetone, which are metal complex salts of known nodicarponyl compounds. Further, no plate-out phenomenon was observed, and workability was extremely good.

Example 2 This example shows that stabilizers (a) to 1 of the present invention were added to a chlorine-containing resin.
A test was conducted to further improve the performance of the resin composition, such as thermal stabilization, by further adding (c) and other known stabilizer components. 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 3.

Compound □ Vinyl chloride resin 100 parts by weight (Zeon 103EP) Epoxidized soybean oil 2.01 barium stearate) 0.6# barium nonyl felt 0.81 zinc stearate)
0.3# Zinc 2-ethylhexoate
0.31 Dicarbonyl compounds in Table 1 0.
II Metal Complex Salts (Table 3) Known Stabilizer Components Table 3 Example 3 This example shows that the stabilizer of the present invention (Table 3)
c) Dynamic thermal stability effect of the resin composition obtained by adding
In particular, in order to approximate actual thermoforming processing, a large-scale roll mill was used, and a long-term rolling test was conducted at a high temperature under an atmosphere directly affected by oxygen under the following formulations and conditions. The results are shown in Table 4.

Below margin (27) Compounded vinyl chloride resin ioo parts by weight (Zeon 1
03EP) Dioctyl phthalate 40 #Epoxidized soybean oil 2.0 #Barium stearate 1.
0.51 overbased barium nonylphenol
0.61 Rethocarbonate Complex Zinc Stearate 0,5I Zinc-p-
Tertiary butyl benzony) 0.21 Diphenyl isooctyl phosphite 0.61 Butylated hydroxytoluene 0.11 Dicarbonyl compounds in Table 1
0.1# Metal complex salt (Table 4) (28) Conditions Steam heating type differential roll mill (diameter 30°5 x length 61cm
IrL), vapor pressure 12 Kf/ctA.

Roll mill rotation ratio and temperature: 20.3 rpm before roll, 16.4 rpm after roll at 185°C surface temperature, 185°C rotation ratio 1:1
．． 24. Nip 0.2 tax Put compound 500F into the above roll mill and knead for a certain period of time (Table 4)
A sheet with a thickness of 0.2 dew was taken each time. Additionally, the sheet deteriorates due to heat on the roll and begins to become colored and sticky. The coloring-adhesion time, processability, etc. were observed.

The results are shown in Table 4.

(29) As is clear from Table 4 above, the stabilizer of the present invention (ω~(
It was found that c) can be subjected to rolling processing for 30 minutes or more, which is the molding condition necessary for industrial processing, and maintains sufficient dynamic thermal stability to the extent that the product can be produced. That is, under these test conditions, if no color deterioration due to heat is observed within 15 to 30 minutes, a molded product that is excellent in industrial practice can be obtained.

Patent applicant: Akishima Chemical Industry Co., Ltd. (31)

Claims (1)

[Scope of Claims] A chlorine-containing resin containing (a) at least one or more organic acid metal salts of barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin, and (c) the following general formula: (In the formula, M is an element from Group 1a of the periodic table, Ua, and Wb.
group, Wb group - Wa group, group (b), group vb or alkylated tin; represents an integer from 1 to 5. )
A stabilized chlorine-containing resin composition obtained by adding a combination of a metal complex salt of a dicarbonyl compound represented by .