JPH05295203A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To provide the subject nontoxic composition excellent in thermal stability. CONSTITUTION:The objective composition can be obtained by making (A) a composition comprising (1) 100 pts.wt. of a vinyl chloride-based resin, (2) <=10 pts.wt. of a plasticizer and (3) an amino acid zinc salt contain (B) at least one kind of compound among (a) poly(>=3) hydric alcoholic compounds, (b) hindered amine compounds and (c) hydrotalcite compounds.

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel vinyl chloride resin composition. More specifically, it relates to a vinyl chloride resin composition that exhibits excellent heat resistance during processing of the vinyl chloride resin. 2. Description of the Related Art Vinyl chloride resin compositions such as polyvinyl chloride are excellent in transparency, strength, processability, colorability, etc., and are inexpensive, so that they can be used as films, sheets, pipes, joints,
Furthermore, in recent years, it has also been used in large amounts in vehicle leather and the like. When vinyl chloride polymer is exposed to light or heat,
Decomposition and deterioration mainly caused by dehydrochlorination reaction,
A conjugated double bond, a so-called polyene structure, is produced and colored. Further, when the decomposition further proceeds, molecular cutting and cross-linking occur, resulting in a decrease in mechanical strength and the like, resulting in embrittlement. Therefore, the dehydrochlorination reaction occurs due to heat during molding,
In order to prevent the color tone of the product from deteriorating or the physical properties of the product from decreasing, the vinyl chloride resin composition contains
Various stabilizers are blended. As the stabilizer, lead,
Organic acid salts such as cadmium, zinc and calcium are most often used. However, in recent years, the toxicity of the lead-based and cadmium-based stabilizers has come to be regarded as a problem, and the use thereof has been considerably restricted. In particular, with regard to pipes used for water pipes and the like, the regulation of the amount of lead elution has been strengthened. Due to these problems, detoxification of plastic additives is avoided, and development of nontoxic stabilizers having thermal stability that can replace lead-based stabilizers is desired. Recently, the use of amino acid zinc compounds has been proposed (for example, JP-A-64-87646 and JP-A-54-5504).
7) The thermal stability was not yet sufficient with the compounding recipes found in these Examples and the like. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a vinyl chloride resin composition containing a novel non-toxic stabilizer and excellent in thermal stability. Means and Actions for Solving the Problems In view of the above situation, the present inventors have made earnest studies. A composition containing 10 parts by weight or less of a plasticizer and an amino acid zinc salt with respect to 100 parts by weight of a vinyl chloride resin, wherein (1) a trihydric or higher polyhydric alcohol compound (2) a hindered amine compound (3) A vinyl chloride resin composition containing at least one hydrotalcite compound. The vinyl chloride resin of the present invention is a vinyl chloride homopolymer or a resin mainly composed of vinyl chloride, for example, vinyl chloride and vinyl acetate, vinylidene chloride, ethylene, propylene, methacrylic acid ester, and urethane resin. It is a copolymer, a graft polymer or a blend with these resins. As the trihydric or higher polyhydric alcohol compound used in the present invention, various compounds can be used without limitation. Examples thereof include pentaerythritol and adipic acid partial ester. These trihydric or higher polyhydric alcohol compounds are used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The hindered amine compound used in the present invention has a molecular weight of 250.
The above 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position, and examples of the substituent at the 4-position include a carboxylic acid residue, an alkoxy group, an aryloxy group, and various other groups. Conceivable. Specific examples of the hindered amine-based compound include the following formulas (I) to (VI).
And the like. In addition to these, any compound having a basic structure of a hindered amine compound can be used without being limited to the above representative examples. These hindered amine compounds are used in an amount of 0.001 to 2.0 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The hydrotalcite compound used in the present invention has a general formula of M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ^n-.
_{x / n} · mH ₂ O (however, M ²⁺ : Mg ²⁺ , Zn ²⁺ , Fe ²⁺ , M
^{n 2+, Co 2+, Ni 2+} , Cu 2+ M 3+: Al 3+, Fe 3+, Cr 3+, Co 3+ A n-: OH -, CO 3 2-, SO 4 2-, NO 3 -,
Cl ⁻ x: 0 <x ≦ 0.33
) Is a compound represented by the specific _{examples, Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O Mg 4 · 5 Al 2 (OH) 13 CO 3 · 3.5H 2 Mg 4.5 Al 2 _{(OH) 13 CO 3 Mg 3.5} Zn 1.0 Al 2 (OH) 13 CO 3 · 3.
5H ₂ O and the like. Commercially available products are Alkamizer 1, Alkamizer 2, Alkamizer 3, Alkamizer 4,
Alkamizer 5, DHT-4A (all manufactured by Kyowa Chemical Industry Co., Ltd.) and the like. These hydrotalcite compounds are used in an amount of 1 to 10 relative to 100 parts by weight of vinyl chloride resin.
It is used in parts by weight, more preferably 0.5 to 5.0 parts by weight. Examples of the amino acid zinc salt used in the present invention include the general formula (R ¹ ) m-Zn- (R ² ) n [wherein, R ¹ is an amino acid residue: R ² is an alkyl group, an alkoxy group and a hydroxyl group. The groups are selected from the group and may be the same or different. m is an integer of 1 to 2, n is an integer of 0 to 1, m + n is 2, and each may be a mixture. The amino acid of the amino acid metal salt represented by the above general formula or the derivative thereof may be any of an aliphatic amino acid, an aromatic amino acid or a heterocyclic amino acid, but in carrying out the present invention, a monoaminomonocarboxylic acid; Oxyamino acids; Sulfur-containing amino acids; Monoaminodicarboxylic acids; Aliphatic amino acids such as diaminomonocarboxylic acids are preferable, glycine and valine are particularly preferable, and vinyl chloride resin 1
00 parts by weight 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight. Furthermore, zinc fatty acid may be added if necessary. Examples of the fatty acid zinc include zinc stearate, zinc palmitate, zinc myristate,
Examples thereof include zinc laurate, zinc octylate and zinc behenate. These fatty acid zinc is vinyl chloride resin 1
It is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 00 parts by weight. As the plasticizer used in the present invention, various ones such as phthalic acid ester, fatty acid dibasic acid ester, trimellitic acid ester, phosphoric acid ester, polyester plasticizer and epoxy plasticizer can be used without limitation. 10 parts by weight or less based on 100 parts by weight of the base resin, more preferably 0 to 5 parts
Parts by weight. Further, in the present invention, a flame retardant, a filler, a heat stabilization aid, an anti-oxidant, an ultraviolet absorber, an epoxy compound, a lubricant, a pigment and the like which have been conventionally used for vinyl chloride resins may be used in combination. Needless to say. EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples. To 100 parts by weight of vinyl chloride resin, 0.05 part by weight of dibenzoylmethane, 0.3 part by weight of decaquisphenyl heptaquis dipropylene glycol octaphosphite, 0.1 part of dilauryl thiodipropionate.
A mixture of parts by weight and the additives shown in Table 1 is kneaded with a kneading roll at 170 ° C. for 5 minutes, and the obtained sheet is put into a gear oven aging tester at 170 ° C. for a predetermined time. The degree of coloring of the sheet after aging was visually evaluated to evaluate the thermal stability. The evaluation of coloring is as follows. ◎ ... Colorless (excellent in thermal stability) ○… Slight brown △… Light brown ×… Partially blackened or brown XX… Blackened or dark brown (inferior in thermal stability) The symbols in each additive column in the table are The following compounds are shown respectively. Polyhydric alcohols 1: Dipentaerythritol Polyhydric alcohols 2: Dipentaerythritol adipate manufactured by Ajinomoto Co., Inc. Trade name Planerizer-ST-210 Hindered amines 1: Sankyomai trade name represented by the above formula (1) Sanol LS-770 hindered amines 2: Ciba Geigy product name represented by the above formula (u), Kimasorb 944FL hydrotalcites 1: Kyowa Chemical Industry Co., Ltd. Mg, Al hydrotalcite compound product name Alkamizer 1 hydrotal Sites 2: Kyowa Chemical Industry Co., Ltd. Mg, Al, Zn-based hydrotalcite compound product name Alkamizer 4 From the results in Table 1 above, it is understood that the thermal stability can be remarkably improved when at least one of the polyhydric alcohol compound, the hindered amine compound and the hydrotalcite compound is used in combination. Furthermore, zinc fatty acid may be added if necessary. As described above, the vinyl chloride resin composition containing the plasticizer of the present invention in an amount of 10 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin is not toxic and is free from amino acid zinc salts. By using one or more of a polyhydric alcohol compound, a hindered amine compound, and a hydrotalcite compound in combination, excellent thermal stability is achieved.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C08K 5/3435 KHL 7242-4J

Claims (1)

What is claimed is: 1. A composition containing 10 parts by weight or less of a plasticizer and an amino acid zinc salt with respect to 100 parts by weight of a vinyl chloride resin, wherein (1) a trihydric or higher polyhydric alcohol compound is added to the composition. (2) Hindered amine compound (3) A vinyl chloride resin composition comprising at least one kind of hydrotalcite compound.