JPH05295202A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To provide the subject nontoxic compound excellent in electrical insulation, thermal stability and high-temperature processability. CONSTITUTION:The objective composition can be obtained by blending (A) a composition comprising (1) 100 pts.wt. of a vinyl chloride-based resin and (2) >=10 pts.wt. of a plasticizer with (B) an amino acid zinc salt compound and a hindered amine compound.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition containing 10 parts by weight or more as a plasticizer excellent in electrical insulation, thermal stability and high temperature processability. It is a thing.

BACKGROUND OF THE INVENTION Vinyl chloride resins containing plasticizers have various stability in order to satisfy the thermal stability and processability during molding and the electrical and mechanical properties of products. Need agents and additives. Among them, in soft vinyl chloride products such as electric wires and insulating tape,
In particular, it requires electrical insulation, thermal stability, and high-temperature processability. Therefore, lead-based stabilizers such as tribasic lead sulfate and lead stearate are mainly used. However, in recent years, due to problems such as stability to the human body and industrial waste, detoxification of plastic additives has been avoided, and non-toxic stabilizers with electrical insulation and thermal stability that can replace lead-based stabilizers. Was desired to be developed. Recently, the use of hydrotalcite compounds as heat stabilizers for vinyl chloride resins has been proposed (for example, JP-A-57-80444, JP-A-58-15550, and JP-A-60-123545). 61-174270), the conventional compounding recipes found in these examples and the like have excellent thermal stability, but there is a problem that foaming occurs during high temperature processing due to the water content in the hydrotalcite system, and it does not foam. Amino acid zinc compounds have been proposed as non-toxic stabilizers (for example, JP-A-64-87646 and JP-A-54-55047), but the thermal stability and electric insulation are not sufficient, and lead stabilizers are in terms of performance. Nothing comparable to is obtained. The present invention provides a vinyl chloride resin composition that does not use a toxic lead-based stabilizer, is non-toxic, does not foam electrically during electrical processing and thermal stability, and does not foam during high temperature processing (good high temperature processability). Has a purpose.

[Wherein R ₁ is an amino acid residue; R ₂ is a group selected from the group consisting of an alkyl group, an alkoxy group and a hydroxyl group, and may be the same or different. m is 1 or 2,
n is 0 or 1 and m + n is 2, which may be a mixture of each.]

The amino acid represented by the above general formula may be any of an aliphatic amino acid, an aromatic amino acid or a heterocyclic amino acid, and particularly preferred are aliphatic monoaminocarboxylic acids such as glycine and valine.
These amino acid zincs are used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The hindered amine compound used in the present invention is a 2,2,6,6-tetraalkylpiperidine derivative having a molecular weight of 250 or more and having a substituent at the 4-position, and the substituent at the 4-position is, for example, a carboxylic acid. Acid residues, alkoxy groups, allyloxy groups and various other groups are possible. 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 0.5 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The hindered amine compound is used in an amount of 0.0005 to 0.5 part by weight, preferably 0.005 to 0.5 part by weight, based on 1 part by weight of zinc amino acid. The vinyl chloride resin composition of the present invention may be blended with a fatty acid zinc, a trivalent or higher polyhydric alcohol compound and a hydrotalcite compound, if necessary. Examples of the fatty acid zinc include zinc stearate,
Examples thereof include zinc palmitate, zinc myristate, zinc laurate, zinc octylate and zinc behenate.
These fatty acid zincs are used in an amount of 0.05 to 5 parts by weight, more preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Examples of hydrotalcite compounds include Mg ₆ Al ₂ (OH) ₁₆ CO ₃
・ 4H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・
3.5H ₂ O Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ , Mg _3.5 Al
₂ (OH) ₁₃ CO ₃ , 3.5H ₂ O and the like,
Commercially available products include Alkamizer 1, Alkamizer 2, Alkamizer 4, and DHT-4A (all manufactured by Kyowa Chemical Industry Co., Ltd.). These hydrotalcite compounds are used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of vinyl chloride, but in order to suppress foaming during high temperature processing and to improve heat resistance, 0 .05 to 0.5
phr is preferred. As the polyhydric alcohol compound having a valence of 3 or more, various compounds can be used without limitation, and examples thereof include ditrimethylolmethane, trimethylolpropane,
Examples thereof include glycerin, mannitol, sorbitol, erythritol, pentaerythritol, dipentaerythritol, dipentaerythritol and adipic acid partial ester. These 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. Further, in the present invention, plasticizers, fillers, heat stabilization aids, antioxidants, ultraviolet absorbers, epoxy compounds, lubricants, pigments 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. Examples 1-6, Comparative Examples 1-5 Polyvinyl chloride (degree of polymerization 1050) 100 parts by weight, DI
A mixture of 50 parts by weight of NP (diisononyl phthalate) and the additives shown in Table 1 was kneaded with a kneading roll at 160 ° C. for 5 minutes, and then the obtained films were overlapped and 170 ° C.
Was pressed for 10 minutes to prepare a press sheet having a thickness of 1 mm. The symbols in the respective additive columns in the table indicate the following compounds, respectively. DPE: dipentaerythritol DBM: dibenzoylmethane hydrotalcite compound HT: Kyowa Chemical Industry Co., Ltd. Mg, Al hydrotalcite compound, trade name Alkamizer 1 amino acid zinc A ₁ = glycine zinc A ₂ = valine zinc hindered amine System compound III: ADEKA ARGUS trade name mark LA-57 represented by the formula (III) V: American Cyanamid trade name Siasorb UV-3346 VI represented by the formula (V): the formula ( VI) represented by Ciba Geigy Co., Ltd. under the trade name Kimasorb 944FL. The obtained press sheet is used to carry out JIS K-6723.
Volume resistivity (measured at 30 ° C) according to the test method described
And thermal stability (measured at 180 ° C) were evaluated, and for high temperature workability, the temperature was set to 21 according to the thermal stability test method.
The same test was performed at 0 ° C., and the bulkiness after 30 minutes was measured. In the evaluation, the higher the bulk, the higher the foamability and the lower the volume, the lower the foamability. The colorability was visually evaluated. The evaluation of colorability is as follows. ⊚: Very good O: Excellent Δ: Slightly inferior ×: Inferior The above results are shown in Table 1. Examples, Comparative Examples Polyvinyl chloride (degree of polymerization: 1300) 100 parts by weight, polyester-based plasticizer (trade name Polycider W-305ELS manufactured by Dainippon Ink and Chemicals, Inc.) 50 parts by weight, heavy calcium carbonate 20 parts by weight, A mixture of 5 parts by weight of titanium oxide and the additives shown in Table 2 was used in the above Examples 1 to 5 and Comparative Examples 1 to 1.
The mixture was kneaded and pressed under the same conditions as in No. 3 to produce a pressed sheet having a thickness of 1 mm. The symbols in the respective additive columns in the table indicate the following compounds, respectively. DHA: Dehitoroacetate DPEAA: Adipic acid partial ester of dipentaerythritol manufactured by Ajinomoto Co., Inc. Hydrotalcite compound HT: Alkamizer 1 amino acid Zn salt compound Al: Glycine Zn salt hindered amine compound I manufactured by Kyowa Chemical Industry Co., Ltd. : Sankyo LS-770 II, a product of Sankyo Co., Ltd. represented by the formula (I): TINUVIN 622LD IV, a product of Ciba-Geigy, represented by the formula (II): Montefloss, represented by the formula (IV) Product name Spinuvex A36 manufactured by using the obtained press sheet, as in Examples 1 to 6 and Comparative Examples 1 to 5, low volume efficiency (measured at 30 ° C.) and thermal stability (measured at 180 ° C.) High temperature processability (measured at 210 ° C.) and colorability were evaluated.
The results are shown in Table 2. From the results of Tables 1 and 2 above, it is understood that when the amino acid Zn salt compound is used in combination with a hindered amine compound, both electrical insulation (low volume efficiency) and thermal stability and high temperature processability can be significantly improved.

As described above, the vinyl chloride resin composition according to the present invention is not toxic because it does not use a lead stabilizer, and moreover, by using an amino acid Zn salt compound and a hindered amine compound in combination. It has electrical insulation, thermal stability and high temperature processability comparable to lead-based stabilizers.

Claims (1)

[Claims] 1. A plasticizer 1 to 100 parts by weight of zinc amino acid, a hindered amine compound and a vinyl chloride resin.
A vinyl chloride resin composition comprising 0 part by weight or more.