JPH0726094A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain a chlorine-contg. resin compsn. which can prevent coloring and decrease in mechanical strength from occurring during molding processing as it exhibits excellent heat stability,with excellent impact resistance and no toxicity or low toxicity. CONSTITUTION:A chlorine-contg. resin compsn. is prepd. by compounding 0.1-3 pts.wt. zinc carboxylate (a), 0.1-3 pts.wt. at least one selected from magnesium, calcium and barium carboxylate (b), 0.01-0.5 pt.wt. dialkyl tin mercaptide (c) and 0.1-3 pts.wt. epoxy group-contg. polymer to 100 pts.wt. chlorine-contg. resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel chlorine-containing resin composition, and more particularly to a non-toxic or low-toxic chlorine-containing resin composition which is excellent in thermal stability and strength.

[0002]

2. Description of the Related Art Generally, a chlorine-containing resin is excellent in processability, weather resistance, and imparting plasticity by adding a plasticizer.
Further, since it is inexpensive, it is widely used as a raw material for various molded products such as films, sheets, tubes, corrugated sheets and pipes. However, this chlorine-containing resin lacks stability to heat and light, and since the molding processing temperature and thermal decomposition temperature are close to each other, thermal decomposition due to dehydrochlorination tends to occur during molding processing, which results in molding products. It causes an unfavorable situation such as coloration of the resin and deterioration of mechanical strength. In order to avoid such a situation, lead-based stabilizers such as tribasic lead sulfate and dibasic lead stearate have been conventionally used in many cases, and improvements in heat stability have been practically made. However, lead compounds are highly toxic,
It is preferable not to use the lead-based stabilizer from the viewpoint of health care of the person who handles it and environmental pollution due to leakage of lead from the molded product. Metal soaps such as calcium soap, barium soap, magnesium soap, and zinc soap are known as non-toxic or low-toxic stabilizers, but these metal soaps have the drawback of not having sufficient thermal stability. . for that reason,
"Elucidation of stabilization of polyvinyl chloride and blending of stabilizing aids
"Actual effect" (March 15, 1984, published by Soft Giken Press) Ca / Zn, Ba / Z
n, Ca / Ba / Zn, etc., a composition aiming at a synergistic effect, and an organophosphorus compound, an epoxy compound, a polyol compound, a sulfur-containing compound, a nitrogen-containing compound, etc. are added to these combinations as a stabilizing aid. Such compositions have been proposed. However, even when using a composition or a stabilizing aid aimed at the synergistic effect of these metal soaps,
There is a problem that the thermal stability is not yet sufficient, and the hard molded product using the metal soap stabilizer has low impact resistance. On the other hand, tin-based stabilizers have low toxicity and excellent thermal stability, but practical compounds are liquids, so when they are used in hard molded products, the strength is unavoidably reduced. Occurs.

[0003]

Under the circumstances, the present invention has been made for the purpose of providing a non-toxic or low-toxic chlorine-containing resin composition which is excellent in thermal stability and strength. It is a thing.

[0004]

Means for Solving the Problems As a result of intensive studies to develop a chlorine-containing resin composition having the above-mentioned preferable properties, the present inventors have found that a chlorine-containing resin contains a specific combination of carboxylic acid inorganic compounds. It was found that a composition in which a salt, a dialkyltin mercaptide and an epoxy group-containing polymer were blended in specific proportions could respectively meet the purpose, and the present invention was completed based on this finding. That is,
The present invention relates to (a) with respect to 100 parts by weight of a chlorine-containing resin.
0.1 to 3 parts by weight of zinc salt of carboxylic acid, (b) 0.1 to 3 parts by weight of at least one selected from magnesium salt, calcium salt and barium salt of carboxylic acid, (c)
Provided is a chlorine-containing resin composition comprising 0.01 to 0.5 part by weight of a dialkyltin mercaptide and 0.1 to 3 parts by weight of a (d) epoxy group-containing polymer.

The present invention will be described in detail below. Examples of the chlorine-containing resin used in the composition of the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, copolymers of vinyl chloride and olefin, and copolymers of vinyl chloride and vinyl acetate. These chlorine-containing resins are 1
One kind may be used, or two or more kinds may be used in combination. In the composition of the present invention, a zinc salt of a carboxylic acid is used as the component (a). Examples of the carboxylic acid include saturated or unsaturated fatty acids having 4 to 24 carbon atoms and 7 to 1 carbon atoms.
Carboxylic carboxylic acids of 6 are preferred, and specific examples of such carboxylic acids include hexanoic acid, octanoic acid, and 2-
Ethyl hexanoic 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, sebacic acid,
Benzoic acid, toluic acid, xylic acid, ethylbenzoic acid,
Examples thereof include p-t-butylbenzoic acid, naphthenic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, anisic acid and salicylic acid.

In the composition of the present invention, the zinc salt of the carboxylic acid, which is the component (a), may be used alone or in combination of two or more. It should be in the range of 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on parts by weight. If the content is less than 0.1 part by weight, the thermal stabilizing effect will not be sufficiently exhibited, and if it exceeds 3 parts by weight, long-term thermal stability will be deteriorated due to zinc burning. In the composition of the present invention, as the component (b), magnesium salt of carboxylic acid,
At least one selected from calcium salts and barium salts is used. As the carboxylic acid constituting the component (b), the same carboxylic acids as those described for the carboxylic acid constituting the component (a) can be mentioned.

In the composition of the present invention, the magnesium salt, the calcium salt and the barium salt of the carboxylic acid as the component (b) may be used alone or in combination of two or more thereof. The blending amount must be in the range of 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the chlorine-containing resin. This blend amount is 0.
If it is less than 1 part by weight, the heat stabilizing effect is not sufficiently exhibited, and if it exceeds 3 parts by weight, the initial colorability is deteriorated. In the composition of the present invention, dialkyltin mercaptide is used as the component (c). Examples of the dialkyl tin mercaptide include those represented by the general formula

[0008]

[Chemical 1]

A compound represented by: In the general formula [1], R ¹ and R ² each have 1 to 2 carbon atoms.
4 straight-chain or branched-chain alkyl groups, which may be the same or different from each other. R ³ and R ⁴ are each a linear or branched alkylene group having 1 to 8 carbon atoms, which may be the same or different. Further, R ⁵ and R ⁶ are each an alkyl group having 1 to 24 carbon atoms or a substituted alkyl group (as a substituent, an alkyl group, an alkoxy group, a phenyl group,
Phenoxy group, etc.), which may be the same or different from each other. Further, R ⁵ and R ⁶ may be bonded to each other at a terminal or a substituent to form a ring. In the composition of the present invention, the dialkyltin mercaptide as the component (c) may be used alone or in combination of two or more, and the amount thereof is 100 parts by weight of the chlorine-containing resin. , 0.01 to 0.5 part by weight, preferably 0.05 to 0.3 part by weight. If the content is less than 0.01 part by weight, the heat stabilizing effect and the impact resistance improving effect will not be sufficiently exerted, and if it exceeds 0.5 part by weight, the heat distortion temperature of the hard molded product will decrease.

In the composition of the present invention, an epoxy group-containing polymer is used as the component (d). The epoxy group-containing polymer may be a homopolymer of a monomer having an epoxy group or a copolymer of another monomer copolymerizable with the monomer having an epoxy group. Examples of the monomer having an epoxy group include unsaturated glycidyl esters, unsaturated glycidyl ethers, and epoxy alkenes. Specifically, glycidyl (meth) acrylate, β-methylglycidyl (meth)
Acrylate, glycidyl itaconate, glycidyl butenylate, glycidyl hexenoate, glycidyl oleate, allyl glycidyl ether, 2-methylallyl glycidyl ether, p-ethylenylphenyl glycidyl ether, propenyl glycidyl ether, p-glycidyl styrene, 3,4 -Epoxybutene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene and the like can be mentioned, and these may be used alone. You may use it in combination of 2 or more type.

On the other hand, as other copolymerizable monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. (Meth) acrylates, styrene, α
-Aromatic vinyl compounds such as methylstyrene, o-chlorostyrene, and vinylnaphthalene; cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile; and maleic acid, vinyl acetate, ethylene, and the like. These are used alone. Alternatively, two or more kinds may be used in combination. The epoxy group-containing polymer as the component (d) preferably has a weight average molecular weight of 2,000 to 300,000 and an epoxy equivalent of 1,500 or less. If this epoxy equivalent exceeds 1,500, the heat stabilizing effect is reduced. In the composition of the present invention, the epoxy group-containing polymer of the component (d) may be used alone or in combination of two or more, and the compounding amount thereof is 100 parts by weight of the chlorine-containing resin. On the other hand, it should be in the range of 0.1 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight. If the blending amount is less than 0.1 part by weight, the heat stabilizing effect is not sufficiently exhibited, and if the blending amount exceeds 3 parts by weight, the heat stabilizing effect is not so much improved for the amount.

The method for preparing the chlorine-containing resin composition of the present invention is not particularly limited. For example, the chlorine-containing resin and (a)
It is possible to use a method in which the respective components of (a) to (d) are simultaneously mixed at once, or first the respective components of (a) to (d) are mixed to prepare a so-called one-pack product, and then this product is mixed with chlorine. Although the method of adding to the contained resin and mixing may be used, from the viewpoint of uniform mixing of the composition, the method of adding to the chlorine containing resin and then mixing is more advantageous from the viewpoint of uniformly mixing the composition.
In the present invention, the amount of the liquid dialkyltin mercaptide is smaller than that of the other components, so that the shape of the one-pack product can be arbitrarily adjusted to a powder to a granular form and added to the chlorine-containing resin. , Easy to mix. In the composition of the present invention, various addition components such as an organic phosphorus compound, an epoxy compound, a polyol compound, a β-diketone compound, a nitrogen-containing compound, and a sulfur-containing compound may be added as desired, as long as the object of the present invention is not impaired. Known stabilizing aids, higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, polyhydric alcohol fatty acid esters such as dipentaerythritol hexastearate, waxes such as paraffin wax, polyethylene wax, montan wax, stearic acid Lubricants such as amides, amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide, fillers such as calcium hydroxide, calcium carbonate, talc and hydrotalcite, and further pigments, antistatic agents, processability improvers , Flame retardant, UV protection And the like may be added.

[0013]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Examples 1 to 4 and Comparative Examples 1 to 6 (1) Preparation and Evaluation of Sheets The components of the types and amounts shown in Table 1 were mixed in advance to prepare a one-pack product, which was a polyvinyl chloride resin. [Daiichi PV
C 103EP, manufactured by Daiichi Vinyl Sales Co., Ltd., average degree of polymerization 10
50] 100 parts by weight to prepare a resin composition,
Using a hot roll having an inch diameter, the mixture was kneaded at 170 ° C. for 3 minutes to prepare a sheet having a thickness of 0.5 mm. Then, this sheet was cut into 5 × 5 cm, and the thermal stability (time until the sheet became black) and the initial colorability (heating 15
The color tone after a minute) was determined. The results are shown in Table 1. With the composition of the present invention, the shape of the one-pack product was a granule with an average particle size of 0.5 mm, and mixing with the resin was possible by an easy method such as mixing with a spoon in a beaker. With a composition using a large amount of the compound, the shape of the one-pack product was a paste, and a powerful mixer such as a mixer was required for mixing with the resin.

[0015]

[Table 1]

[0016]

[Table 2]

Note 1) Average molecular weight 34,000 2) Glycidyl methacrylate (GMA) / methyl methacrylate (MMA) copolymer (weight ratio 50/50),
Average molecular weight 10,000 3) High Wax 220 [manufactured by Mitsui Petrochemical Industry Co., Ltd.] 4) In the case of granules, average particle size 0.5 mm From Table 1, the composition of the present invention (Examples 1 to 4) It can be seen that the composition exhibits the same thermal stability as the composition using a large amount of the tin compound (Comparative Example 5) and the composition using the lead compound (Comparative Example 6). Further, among the constituent components of the present invention, (a) to
It can be seen that the thermal stability or the initial colorability deteriorates even if any one of the components of (d) is omitted (Comparative Examples 1 to 4).

(2) Molding and evaluation of pipe A resin composition was prepared in the same manner as in the above (1), and a Laboplast mill tester [manufactured by Toyo Seiki Seisakusho Ltd., 30C15] was used.
0] was used to extrude the pipe. The extrusion conditions are as follows. Screw: Bi-directional, parallel type, L / D = 2
5 Die: VP-20 Set temperature: C1; 160 ° C, C2; 170 ° C, C3; 17
5 ° C., D; 170 ° C. Screw rotation speed: 40 RPM Table 2 shows the characteristic values during extrusion and the strength of the molded pipe.

[0019]

[Table 3]

From Table 2, the composition of the present invention (Examples 1 to 1)
It can be seen that 4) shows the same extruded state and pipe strength as the composition using the lead compound (Comparative Example 6). Further, it can be seen that the Vicat softening point (heat distortion temperature) is higher than that of the composition using a large amount of tin compound (Comparative Example 5). Further, among the components of the present invention, (a)-
It can be seen that even if any one of the components of (d) is removed, the color tone and falling weight strength (impact resistance) of the pipe are deteriorated (Comparative Examples 1 to 1).
4).

[0021]

The chlorine-containing resin composition of the present invention is excellent in thermal stability, so that it is possible to prevent coloring and deterioration of mechanical strength that occur during molding. Further, since the composition of the present invention has excellent impact resistance and a high heat softening temperature, it can be used for a hard molded product which is required to have these properties. further,
Since the composition of the present invention is nontoxic or low in toxicity, it is suitable for use in applications where toxicity is regulated.

Claims (1)

[Claims] 1. To 100 parts by weight of a chlorine-containing resin,
(A) 0.1 to 3 parts by weight of carboxylic acid zinc salt, (b) 0.1 to 3 parts by weight of at least one selected from magnesium salt, calcium salt and barium salt of carboxylic acid,
A chlorine-containing resin composition comprising (c) 0.01 to 0.5 parts by weight of a dialkyltin mercaptide and (d) 0.1 to 3 parts by weight of an epoxy group-containing polymer.