JPH05247299A - Stabilized vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having not only an esp. low toxicity but also an excellent thermal stability. CONSTITUTION:The title compsn. is prepd. by compounding a vinyl chloride resin with magnesium oxide, magnesium carbonate and/or magnesium hydroxide, calcium oxide and/or calcium hydroxide, and a zinc salt of an org. acid (e.g. zinc benzoate, zinc p-tert-butylbenzoate, zinc octanoate, zinc laurate, or zinc stearate). The compsn. is resistant to thermal discoloration and stable for a considerably long time even at a temp. as high as 200 deg.C.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is novel and useful,
The present invention relates to a stabilized vinyl chloride resin composition. More specifically, the present invention comprises blending a vinyl chloride resin with a specific magnesium compound and calcium compound, respectively, and an organic acid zinc salt. It relates to a stabilized vinyl chloride resin composition which is difficult.

[0002]

2. Description of the Related Art Vinyl chloride resins are resins that are unstable to heat and light, and are particularly prone to thermal deterioration mainly due to dehydrochlorination reaction during heat molding.

Therefore, the molded products of such resins inevitably suffer from disadvantages such as coloring and deterioration of mechanical quality. In order to eliminate these disadvantages, so-called metal soap-based stabilizers such as lead stearate, cadmium stearate, calcium stearate, barium stearate or zinc stearate, or alkyl tin compounds have been used.

[0004]

However, in recent years, these metal salts, especially cadmium salts, have great toxicity problems, and therefore their use is significantly limited.

Therefore, it has been proposed to use various metal salt compounds other than cadmium salts in various combinations, such as barium / zinc soap type stabilizers or calcium / zinc soap type stabilizers. .

However, the performance of the stabilizers in these classes is not sufficient.
Recently, there has been a demand for the development of a calcium / zinc soap-based stabilizer having low toxicity and excellent thermal stability.

[0007]

Therefore, the present inventor has made diligent studies in view of the present circumstances, and as a result, as a result, a specific magnesium chloride compound and a specific calcium compound were added to a specific vinyl chloride resin. The present invention was found here by finding that a vinyl chloride resin composition having an extremely high thermal stability, which is free from toxicity, can be obtained by using a combination with an organic acid zinc salt. It came to completion.

That is, the present invention relates to a vinyl chloride resin, at least one compound (a) selected from the group consisting of magnesium oxide, magnesium carbonate and magnesium hydroxide, and calcium oxide and / or hydroxide. It is an object of the present invention to provide a stabilized vinyl chloride-based resin composition having extremely high practicability, which is formed by mixing calcium (b) and an organic acid zinc salt (c).

[0009]

[Structure] The present invention will be described in detail below.
First, of the above-mentioned magnesium oxide, magnesium carbonate and / or magnesium hydroxide compounds used in the present invention, it is particularly desirable to use magnesium oxide, and the amount of the compound (a) used is
For 100 parts by weight of the vinyl chloride resin (a), 0.
A range of 05 to 5 parts by weight, preferably 0.2 to 3 parts by weight is suitable.

Next, the amount of the above-mentioned calcium oxide and / or calcium hydroxide (b) used in the present invention is 1% of that of the vinyl chloride resin (a).
Within the range of 0.05 to 5 parts by weight with respect to 00 parts by weight,
Preferably, the range of 0.2 to 3 parts by weight is suitable.

Further, as the organic acid constituting the above-mentioned organic acid zinc salt (c) used in the present invention, it is particularly preferable to use a monocarboxylic acid, and among them, only typical ones are exemplified. In addition, acetic acid, dihydroacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neooctanoic acid, 2
-Ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid,
Palmitic acid, stearic acid, isostearic acid, 2-
Hydroxystearic acid, behenic acid, montanic acid,

Benzoic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-t.
ert-Butyl-4-hydroxy-benzoic acid, monochlorobenzoic acid, aminobenzoic acid, acetoxybenzoic acid or N, N-dimethylaminobenzoic acid, or toluic acid, cumic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid. , Elaidic acid, linoleic acid, linolenic acid, neodecanoic acid, soybean oil fatty acid, castor oil fatty acid, tall oil fatty acid, coconut oil fatty acid, dehydrated castor oil fatty acid or bran oil fatty acid.

The amount of the organic acid zinc salt (c) used is 100 parts by weight of the vinyl chloride resin (a).
Within the range of 0.05 to 5 parts by weight, preferably 0.2 to
A suitable range is 3 parts by weight.

The addition ratio of both components (a) and (b) to the vinyl chloride resin is a weight ratio of (a) / [(a) + (b)]. Therefore,
Within the range of 0.1 to 0.9, preferably 0.3.
It is within the range of 0.7.

This is because, when it is less than 0.1 and when it exceeds 0.9, the effect of thermal stabilization tends to be insufficient in general.

Further, the addition ratio of the three components of the component (a) and the component (b) and the above-mentioned component (c) to the vinyl chloride resin is (c) / [( a) + (b)
+ (C)], the weight ratio is in the range of 0.05 to 0.8, preferably in the range of 0.1 to 0.6.

This is because, when it is less than 0.05 or more than 0.8, the effect of thermal stabilization tends to be insufficient in general.

The resin composition of the present invention thus obtained may further contain an organic phosphite compound and / or an epoxy compound, and by combining these compounds, a more excellent synergistic effect can be obtained. Exert.

Of these compounds, first of all, only representative examples of the organic phosphite-based compounds will be exemplified. Diphenyldecylphosphite, triphenylphosphite, trioctylphosphite, tris (nonylphenyl). ) Phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite,
Diphenyloctyl phosphite, tributyl phosphite, dilauryl acid phosphite, diphenyl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl phosphite,

Dioctylphenylphosphite, didecylphenylphosphite, di-p-tert-butylphenyloctylphosphite, bis (neopentylglycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, Tris (lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris (2′-methyl-5′-tert-butyl-4′-oxyphenyl) butanediphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tris (4-oxy-2,5-di -ter
t-butylphenyl) phosphite, tris (4-oxy-3-ethylhexyldiphenyl) phosphite, tris (mono-, di- or mixed nonylphenyl) phosphite,

Hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis [4,
4'-n-butylidene bis (2-tert-butyl-5
-Methylphenol)] thiodiethanoldiphosphite, bis (octylphenyl) .bis [4,4'-n-
Butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl 4,4'-isopropylidene diphenol-pentaerythritol diphosphite, phenyldiisodecyl phosphite, tetratridecyl -4,4'-
n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite or tris (2,4-
Di-tert-butylphenyl) phosphite and the like.

The amount of the compound added is 0.0 with respect to 100 parts by weight of the vinyl chloride resin (a).
A range of 1 to 5 parts by weight, preferably a range of 0.1 to 3 parts by weight is suitable.

Further, only representative examples of the above-mentioned epoxy compounds are exemplified, and epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxy. Linseed oil butyl, epoxidized tall oil fatty acid ester, epoxidized polybutadiene, epoxidized methyl stearate,
Epoxidized ethyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, bisphenol A diglycidyl ether, dicyclopentadiene diepoxide or 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate. .

The addition amount of the compound is 0.0 with respect to 100 parts by weight of the vinyl chloride resin (a).
A range of 1 to 10 parts by weight, preferably 0.5 to 5 parts by weight is suitable.

In the resin composition of the present invention, compounds such as aliphatic carboxylic acid calcium salt, aromatic carboxylic acid calcium salt, aliphatic carboxylic acid barium salt or aromatic carboxylic acid barium salt may be added, if desired. , Used.

In the resin composition of the present invention, if necessary, phthalic acid esters or other ester plasticizers; polyester plasticizers; phosphoric acid ester plasticizers;
Alternatively, various plasticizers including chlorine-based plasticizers can be used, and these are appropriately selected according to the application.

Since adding an antioxidant to the resin composition of the present invention increases the ability to prevent oxidative deterioration of the resin composition, the use of such an antioxidant is appropriately selected depending on the purpose of use. Is recommended.

As the antioxidants, only typical ones are phenolic antioxidants and sulfur-containing compounds.

If an ultraviolet absorber is added to the resin composition of the present invention, the photostability can be further improved. Therefore, depending on the purpose of use, the use of such an ultraviolet absorber can be appropriately used. Is recommended.

As the UV absorbers, only typical ones are exemplified. Benzophenone-based, benzotriazole-based, salicylate-based or substituted acrylonitrile-based, and various metal salts such as nickel or chromium; or Various metal chelates such as nickel or chromium; or triazine type or piperidine type.

In addition to the above, the resin composition of the present invention comprises:
If necessary, further, a crosslinking agent, a pigment, a filler, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a lubricant, a flame retardant, a fluorescent agent, a fungicide, a bactericide, Various additives such as a metal deactivator, a photodegradation agent, a processing aid or an auxiliary agent can also be used.

The vinyl chloride resins used in the present invention are not limited to the typical ones, but polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber,
Vinyl chloride-vinyl acetate-based copolymers, vinyl chloride-ethylene-based copolymers, vinyl chloride-propylene-based copolymers, vinyl chloride-styrene-based copolymers, vinyl chloride-isobutylene-based copolymers , Vinyl chloride-vinylidene chloride-based copolymers, vinyl chloride-styrene-maleic anhydride terpolymers, vinyl chloride-styrene-acrylonitrile terpolymers,

Vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-butadiene copolymers, vinyl chloride-isoprene copolymers, vinyl chloride-chlorinated propylene copolymers, Vinyl chloride-acrylic acid ester-based copolymers, vinyl chloride-maleic acid ester-based copolymers, vinyl chloride-methacrylic acid ester-based copolymers or vinyl chloride-acrylonitrile-based copolymers Halogen-containing synthetic resins;

Alternatively, with the above-mentioned halogen-containing synthetic resins; various α-olefin polymers such as polyethylene, polypropylene, polybutene or poly-3-methylbutene, or ethylene-vinyl acetate copolymers or ethylene. -Polyolefins such as propylene-based copolymers and their copolymers; polystyrene or acrylic resins and the like, styrene, and other (non-styrene) monomers such as maleic anhydride, butadiene or acrylonitrile. Copolymers with polymers; such as acrylonitrile-butadiene-styrene terpolymer, acrylic ester-butadiene-styrene terpolymer or methacrylic acid ester-butadiene-styrene terpolymer Blends with various halogen-free copolymers Etc. it is.

The resin composition of the present invention thus obtained can be used for preparing various PVC extrusion molded articles such as footwear and electric wires.

[0036]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described more specifically. In the following, all parts and% are based on weight unless otherwise specified.

Examples 1 to 10 and Comparative Examples 1 to 3 To 100 parts of "Zeon 102P" [vinyl chloride resin manufactured by Nippon Zeon Co., Ltd.], dibutyl octyl.
80 parts of phthalate (DOP), 1 part of diphenyl octyl phosphite and 4 parts by weight of titanium oxide,
The stabilizers were blended with the specified amount as shown in Table 1.

Then, this was kneaded with a 6 inch roll at 140 ° C. for 5 minutes to prepare a sheet having a thickness of 1.2 mm. After that, the sheet thus obtained is placed on an aluminum foil, covered with the aluminum foil, placed in a 1 mm thick mold which has been heated to 200 ° C. in advance, and a press at 200 ° C. is used. A press heat resistance test was conducted.

This press heat resistance test was observed every 10 minutes. The results are shown in Table 1 and Table 2, respectively, showing the color of the sheet after 10 minutes and the time it took to turn black or brown.

[0040]

[Table 1]

<< Footnotes in Table 1 >> MgO: Abbreviation of magnesium oxide CaO: Abbreviation of calcium oxide St-Zn: Abbreviation of zinc stearate La-Zn: Zinc laurate Abbreviation of Oc-Zn ... Abbreviation of zinc octylate Ben-Zn ... Abbreviation of zinc benzoate

[0042]

[Table 2]

<< Footnotes in Table 2 >> Results of press heat resistance test at 200 ° C.

[0044]

[Table 3]

[0045]

[Table 4]

Examples 11 to 17 The desired resin compositions were obtained in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 3 except that the formulation was changed as shown in Table 1. The test result was obtained. The results are likewise shown in Tables 1 and 2.

[0047]

[Table 5]

<< Footnote of Table 1 >> La-Zn ... Abbreviation of zinc laurate Ben-Zn ... Abbreviation of zinc benzoate

[0049]

[Table 6]

<< Footnotes in Table 2 >> Results of press heat resistance test at 200 ° C.

Examples 18 to 21 and Comparative Examples 4 and 5 In the same manner as in Examples 1 to 10 and Comparative Examples 1 to 3 except that the formulations shown in Table 1 were changed, the desired resin composition was obtained. And obtained test results. The results are likewise shown in Tables 1 and 2.

[0052]

[Table 7]

<< Footnote of Table 1 >> St-Zn: Abbreviation of calcium stearate St-Mg: Abbreviation of magnesium stearate

[0054]

[Table 8]

[0055]

[Table 9] Examples 22 to 27 and Comparative Examples 6 to 9 The formulations obtained according to the formulation recipe as described below were
The mixture was kneaded with a 6-inch roll at 5 ° C. for 5 minutes and then taken out.

Next, 100 g of a cleaning compound as described below was put into each kneaded product and kneaded for 5 minutes to take out a sheet having a thickness of 1 mm. Thus, the stain of the roll due to the stabilizer (that is, plate-out) was observed by the color of the sheet of the cleaning compound, and the evaluation was judged by the judgment criteria as shown below.

"Zeon 103EP" [100 parts vinyl chloride resin manufactured by Nippon Zeon Co., Ltd.] "Polycizer W-2300" [Polyester plasticizer manufactured by Dainippon In 50 Kiki Chemical Industry Co., Ltd.] "Plastron・ Supra Red A9752 ”1〃 [Red pigment manufactured by Dainippon Ink and Chemicals, Inc.] Test additive shown in Table 3 x〃

Cleaning compound "Zeon 103EP" 100 parts Dioctyl phthalate 50〃 Stearic acid 0.5〃 "GREC T-135" [Butyl tin stabilizer of Dainippon Ink and Chemicals Co., Ltd. 2.0〃] Titanium oxide 1.0〃

○: The sheet color is white, that is, there is no plate-out. X ... The sheet color is red, that is, there is plate-out.

[0060]

[Table 10]

<< Footnotes in Table 3 >> St-Zn ... Abbreviation of calcium stearate La-Zn ... Abbreviation of zinc laurate St-Mg .... Abbreviation of magnesium stearate St-Ca .... Calcium stearate Abbreviation for La-Ca ... Abbreviation for calcium laurate

[0062]

[Table 11]

[0063]

[Table 12]

[0064]

[Table 13]

[0065]

EFFECTS OF THE INVENTION The resin composition of the present invention is highly practical because it is hardly colored even at a high temperature of 200 ° C.

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[Procedure amendment]

[Submission date] March 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

Examples 1 to 10 and Comparative Examples 1 to 3 To 100 parts of "Zeon 102P" [vinyl chloride resin manufactured by Nippon Zeon Co., Ltd.], dibutyl octyl.
80 parts of phthalate (DOP) and 4 parts of titanium oxide were compounded with a predetermined amount of stabilizers as shown in Table 1.

[Procedure amendment]

[Submission date] April 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

Examples 1 to 10 and Comparative Examples 1 to 3 To 100 parts of "Zeon 102P" (vinyl chloride resin manufactured by Nippon Zeon Co., Ltd.), 80 parts of dioctyl phthalate (DOP) and titanium oxide were added. 4 parts and a predetermined amount of stabilizers as shown in Table 1 were blended.

Claims (1)

[Claims] 1. At least one compound (a) selected from the group consisting of magnesium oxide, magnesium carbonate and magnesium hydroxide with respect to a vinyl chloride resin.
A stabilized vinyl chloride resin composition, comprising: a calcium oxide and / or calcium hydroxide (b) and an organic acid zinc salt (c).