JPH06248142A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin nontoxic or lowly toxic composition excellent in heat stability and long-term discoloration resistance by mixing a vinyl chloride resin with a plurality of specified compounds. CONSTITUTION:This resin composition is prepared by mixing desirably 100 pts.wt. vinyl chloride resin with desirably 0.01-10 pts.wt. at least one compound (e.g. calcium stearate) selected from among Ca salts, Ba salts, Zn salts and Mg salts of carboxylic acids and desirably 0.01-5 pts.wt. at least one compound (e.g. triethanolamine/ethylene oxide adduct) selected from among an alkanolamine, an alkylamine and a polyamine/epoxy compound adduct.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a non-toxic or low-toxic vinyl chloride resin composition having excellent thermal stability.

[0002]

2. Description of the Related Art Generally, vinyl chloride resins are
It is widely used as a raw material for various molded products such as films, sheets, tubes, corrugated sheets and pipes because it is excellent in weather resistance and imparts plasticity by adding a plasticizer and is inexpensive. However, vinyl chloride resin lacks heat and light stability, and since the molding processing temperature and thermal decomposition temperature are close to each other, thermal decomposition due to dehydrochlorination is likely to occur during molding processing. And the mechanical strength is reduced. In order to prevent this, zinc-based, lead-based, alkaline earth metal-based or tin-based organometallic stabilizers are mainly added to vinyl chloride resins, but lead-based and cadmium-based stabilizers are not toxic. Highly restricted in its use. Further, zinc and alkaline earth metal-based stabilizers, which have low toxicity, do not have sufficient thermal stability for a long time and cause coloration during the molding process, and therefore improvement of the thermal stability is strongly demanded. Various studies have been proposed for improving the thermal stability of these organometallic compound stabilizers. For example, "Elucidation of Stabilization of Polyvinyl Chloride and Actual Conditions of Mixing / Effect of Stabilizing Aid" (March 15, 1984, published by Soft Giken Publishing Co., Ltd.) describes Ca / Zn, Ba / Zn, Mg / Due to the synergistic effect of the combination of Zn, a composition for the purpose of preventing thermal discoloration properties, and further a combination of these, as a stabilizing aid, an organophosphorus compound, an epoxy compound, a polyol compound, a β-diketone compound, a sulfur-containing compound Although a composition containing such additives has been proposed, improvement in thermal stability is not yet sufficient. Further, as thermal stabilizing aids, amines, amides, isocyanurates, hydrazides, nitrogen-containing compounds such as nitro compounds, and polyhydric alcohol adducts of epoxy compounds have been proposed. For example, Japanese Patent Publication Sho 5
No. 2-30175 discloses an improvement in thermal stability by using an inorganic metal stabilizer in combination with an alkanolamine or polyarylamine, and in Japanese Patent Publication No. 53-42349 discloses a heat stability by using a combination of metal soap and hydrazine. Improvements are proposed. Further, JP-B-58-40581 discloses the improvement of stability by the combined use of a metal soap and a polyhydric alcohol adduct of an epoxidized fatty acid ester, and JP-B-59-28.
Japanese Patent No. 228 proposes improvement of thermal stability by the combined use of a metal soap and a polyhydric alcohol adduct of dihydric phenol glycidyl ether. However, even in these technologies, the improvement of thermal stability is still insufficient and has not reached the level of practical use.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and an object thereof is to provide a non-toxic or low-toxic vinyl chloride resin composition excellent in thermal stability. Is.

[0004]

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a specific carboxylic acid metal salt and a specific epoxy compound adduct are used in combination with a vinyl chloride resin. It was found that the thermal stability can be greatly improved, and the present invention has been completed based on this finding.

That is, according to the present invention, (a) at least one compound selected from calcium salt, barium salt, zinc salt and magnesium salt of carboxylic acid and (b) alkanolamine epoxy compound are added to vinyl chloride resin. At least one selected from the group consisting of polyamine epoxy compound adducts and polyamine epoxy compound adducts.
Stabilized vinyl chloride resin composition comprising at least one compound, and (a) calcium salt, barium salt, zinc salt and magnesium salt of carboxylic acid to vinyl chloride resin And at least one compound selected from (b) alkanolamine epoxy compound adduct, alkylamine epoxy compound adduct and polyamine epoxy compound adduct, and (c) polyol compound. The present invention provides a stabilized vinyl chloride resin composition characterized by the following. The vinyl chloride resin to which the composition of the present invention is applied is a resin containing a vinyl chloride monomer as a main component, and examples thereof include known vinyl chloride monomers such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer. A resin containing as a main component can be used.

The carboxylic acid group constituting the calcium salt, barium salt, zinc salt and magnesium salt of the carboxylic acid as the component (a) of the composition of the present invention has, for example, 4 to 2 carbon atoms.
4 saturated fatty acids or unsaturated fatty acids, carbocyclic carboxylic acids having 7 to 16 carbon atoms, specifically, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, palmitooleic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid,
Adipic acid, pimelic acid, glutaric acid, azelaic acid,
One or two of sebacic acid, benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthenic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, anisic acid, salicylic acid, etc. Mixtures of more than one can be used. The addition amount of these metal salts of organic carboxylic acids can be 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin.

Examples of the alkanolamine constituting the alkanolamine-epoxy compound adduct of the component (b) of the present invention include triethanolamine, diethanolamine, ethanolamine, triisopropanolamine, diisopropanolamine, isopropanolamine, tri-n. -Propanolamine, di-n-propanolamine, n-propanolamine, tris (dihydroxypropyl) amine, diisopropanolethanolamine, isopropanolethanolamine, dihydroxypropylamine, bis (dihydroxypropyl)
Amine and the like can be used. Examples of the alkylamine constituting the alkylamine epoxy compound adduct include:
There are alkylamines having an alkyl group having 1 to 24 carbon atoms such as methylamine, ethylamine, propylamine, octylamine and stearylamine. As the polyamine constituting the polyamine epoxy compound adduct, use ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, etc. You can

Epoxy compounds added to these amines include ethylene oxide, propylene oxide,
Alkylene oxides such as styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether,
Phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl alcohol glycidyl ether, glycerol glycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol (n = 2-20) glycidyl ether, polyglycerol (n = 2-20) ) Polyglycidyl (n = 2 to 22) ether, ethylene glycol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol (n = 2 to 50)
Glycidyl ether, polyethylene glycol (n = 2
To 50) diglycidyl ether, propylene glycol glycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol (n = 2 to 2)
5) Glycidyl ether, polypropylene glycol (n = 2 to 25) diglycidyl ether, neopentyl glycol glycidyl ether, neopentyl glycol diglycidyl ether, polyneopentyl glycol (n = 2 to 20) glycidyl ether, polyneopentyl glycol ( n = 2 to 20) diglycidyl ether,
Pentaerythritol glycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, polypentaerythritol (n
= 2 to 10) glycidyl ether, polypentaerythritol (n = 2 to 10) polyglycidyl (n = 2 to 2)
2) Ethers, glycidyl ethers such as sorbitol glycidyl ether, sorbitol polyglycidyl (n = 2 to 6) ether, trimethylpropane glycidyl ether, trimethylpropane diglycidyl ether, trimethylpropane triglycidyl ether, sorbic acid glycidyl ester, 2-ethylhexyl Acid glycidyl esters, malonic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, maleic acid diglycidyl ester, itaconic acid diglycidyl ester, dimer acid diglycidyl ester,
Glycidyl esters such as phthalic acid diglycidyl ester, glycidol and the like can be used. For the addition of the epoxy compound to the amines, one kind or two or more kinds may be used together with the amines and the epoxy compounds. Further, the addition of the epoxy compound may be block or random.
These compounds may be used alone or in combination of two or more. The addition amount of these amine epoxy compound adducts is
0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, can be added to 100 parts by weight of the resin.

Examples of the polyol compound of the component (c) of the present invention include glycerin, diglycerin, sorbitol, mannitol, xylitol, pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolpropane, polyglycerin, polyethylene glycol, polyvinyl alcohol. Or a partial ester of these compounds with a saturated fatty acid or unsaturated fatty acid having 4 to 24 carbon atoms and a carbocyclic carboxylic acid having 7 to 16 carbon atoms, and the like can be used. The addition amount of these polyol compounds is 0.0 with respect to 100 parts by weight of the resin.
1 to 5 parts by weight, preferably 0.1 to 3 parts by weight can be added. In the production of the composition of the present invention, the above components can be added to a vinyl chloride resin and kneaded by heating, but the order of addition of the added components is not particularly limited, and the components are appropriately added and mixed. be able to. Also,
When the polyol compound of the component (c), which is optionally added, is added to the composition of the present invention, the amine epoxy compound adduct of the component (b) and the polyol compound of the component (c) are separately prepared. In addition to the method of adding to the resin composition, before adding to the resin composition, first, a melt mixture of both components (b) and (c) is prepared, and then it is suitable for a production method of adding this to a vinyl chloride resin. Can be manufactured. By this manufacturing method, an excellent heat stable composition can be obtained. In addition, the composition of the present invention,
Organic phosphorus compound, epoxy compound, β-diketo compound,
Well-known stabilizing aids such as nitrogen-containing compounds, sulfur-containing compounds and inorganic metal compounds, higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, paraffin wax, polyethylene wax, waxes such as montan wax, stearic acid amide, Lubricants such as amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide, phthalic acid ester-based, adipic acid ester-based, aliphatic polyester-based, plasticizers such as epoxidized soybean oil, calcium hydroxide, calcium carbonate, Use fillers such as talc and hydrotalcite, as well as pigments, antistatic agents, processability improvers, flame retardants, UV inhibitors, antioxidants, etc., unless they impair the thermal stability improving effect of the present invention. You can

[0010]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. [Preparation of Sample Sheet] A vinyl chloride resin composition containing the following formulation 1 to 3 and the sample shown in Table 1 was kneaded at 160 ° C. for 5 minutes using a hot roll having a diameter of 9 inches to obtain a thickness. I made a 1mm sheet. [Thermal stability evaluation method] Cut the sample sheet into 4 x 6 cm,
Heating was performed in a gear oven at 185 ° C. The thermal stability was evaluated by the time required for the sample sheet to turn black. [Melting Method for Preparing Melt Mixture] The melt mixture of the amine-epoxy compound adduct and the polyol compound used in the formulation 3 is a polyol compound having a melting point of 10 to 20 ° C.
After being melted at a high temperature, an amine-epoxy compound adduct was added and uniformly mixed, and then cooled and ground, and then used. In the following formulation, the amine-epoxy compound adduct and the polyol compound shown in Table 1 were used in the indicated amounts.

Formulation 1 (Examples 1 to 16 and Comparative Examples 1 to 6) Polyvinyl chloride resin [Daiichi PVC Sales Co., Ltd., 103EP] 100 parts by weight Calcium stearate 0.5 parts by weight Zinc stearate 0.5 Part by weight Polyethylene wax [Mitsui Petrochemical Industry Co., Ltd., Hi-Wax220] 0.5 part by weight Amine epoxy compound adduct Predetermined amount Polyol compound Predetermined amount

Formulation 2 (Examples 17 to 19, Comparative Examples 7 and 8) Polyvinyl chloride resin [Daiichi Polyvinyl chloride Co., Ltd., 103EP] 100 parts by weight Magnesium stearate 0.5 parts by weight Zinc stearate 0. 5 parts by weight Polyethylene wax [Mitsui Petrochemical Industry Co., Ltd., Hi-Wax 220] 0.5 parts by weight Amine epoxy compound adduct Predetermined amount Polyol compound Predetermined amount

Formulation 3 (Examples 20 to 23) Polyvinyl chloride resin [Daiichi Polyvinyl chloride Co., Ltd., 103EP] 100 parts by weight Calcium stearate 1.0 parts by weight Zinc stearate 1.0 parts by weight Stearic acid 0.0. 2 parts by weight Polyethylene wax [Hi-Wax 220, Mitsui Petrochemical Industry Co., Ltd.] 0.5 parts by weight Melt mixture of amine-epoxy compound adduct and polyol compound Predetermined amount Evaluation results are shown in Table 1.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

The vinyl chloride resin composition of the present invention is excellent in thermal stability.

[0018]

Since the vinyl chloride resin composition of the present invention is excellent in thermal stability and long-term discoloration preventive property, it is possible to prevent discoloration and deterioration of mechanical strength that occur during molding. further,
INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention is non-toxic or low-toxic, and thus can be used in applications where toxicity is regulated.

Claims (2)

[Claims] 1. A vinyl chloride resin containing (a) at least one compound selected from calcium salts, barium salts, zinc salts and magnesium salts of carboxylic acids, and (b) alkanolamine epoxy compound adducts, alkylamines. A stabilized vinyl chloride resin composition comprising at least one compound selected from an epoxy compound adduct and a polyamine epoxy compound adduct. 2. A vinyl chloride resin containing (a) at least one compound selected from calcium, barium, zinc and magnesium salts of a carboxylic acid, and (b) an alkanolamine epoxy compound adduct, an alkylamine. A stabilized vinyl chloride resin composition, comprising at least one compound selected from an epoxy compound adduct and a polyamine epoxy compound adduct, and (c) a polyol compound.