JP2672117B2 - Halogen-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a halogen-containing resin composition. More specifically, it relates to a halogen-containing resin composition having excellent heat stability, anti-coloring property and heat resistance.

<Prior Art> Generally, a halogen-containing resin, particularly a vinyl chloride resin, is easily deteriorated by the action of heat and light, and as a result, discoloration, decomposition, deterioration of mechanical strength, change in appearance, deterioration, etc. The product value of the product is reduced, and problems such as inability to withstand long-term use occur.

JP-A-54-55,047 discloses that a vinyl chloride resin is mixed with an amino acid metal salt or a derivative thereof to form a composition having excellent thermal stability. It has been revealed that the amino acid metal salt or its derivative is considerably excellent not only in heat stability but also in processability. As the amino acid metal salt, calcium salt, zinc salt and the like are used, and they have advantages such as an extremely long stabilization time, an extremely short dehydrochlorination rate, and relatively little physiological toxicity.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel halogen-containing resin composition.

Another object of the present invention is to provide a halogen-containing resin composition which is more excellent in heat stability, heat resistance and coloration prevention than a halogen-containing resin composition containing only an amino acid metal salt or a derivative thereof. is there.

Still another object of the present invention is, as compared with a halogen-containing resin composition containing only an amino acid metal salt or a derivative thereof,
Another object of the present invention is to provide a halogen-containing resin composition having improved molding processability.

Still other objects and advantages of the present invention will be apparent from the following description.

According to the invention, such objects and advantages of the invention are: (A) 100 parts by weight of a halogen-containing resin (B) at least one first zinc salt selected from the group consisting of zinc salts of glycine and zinc salts of glutamic acid.
0.1 to 10 parts by weight (C) At least one of basic zinc salt of organic carboxylic acid
This is achieved by a halogen-containing resin composition consisting of an intimate mixture of 0.01 to 5 parts by weight of the second zinc salt of the seed and (D) 0.01 to 5 parts by weight of melamine.

Examples of the halogen-containing resin (A) in the composition of the present invention include polyvinylidene chloride, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, brominated polyethylene. , Rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-
Propylene copolymer, vinyl chloride-styrene copolymer,
Vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer , Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid copolymer, etc. Or a polymer obtained by halogenating a polyolefin,
Examples thereof include copolymers of halogenated resins, and polymer blends of these halogen-containing resins with ABS resins, MBS resins, EVA resins, butadiene, urethane vinyl acetate and the like.

Among these, polyvinyl chloride, chlorinated polyethylene, vinyl chloride vinyl acetate copolymer, vinyl chloride ethylene copolymer and polyvinyl chloride and ABS resin, MBS resin,
Particularly preferred is a polymer blend with EVA resin or polyurethane.

Zinc salt of glycine and zinc salt of glutamic acid (B)
As the salt, for example, a salt containing 0.8 to 3 equivalents of zinc per 1 equivalent of the carboxyl group of glycine or glutamic acid is preferably used. Of these, particularly preferably,
It is an equivalent salt or basic salt in which zinc is present in about equivalent to 2 equivalents per equivalent of the carboxyl group of glycine or glutamic acid.

The zinc salt (B) can be produced by reacting glycine or glutamic acid with, for example, zinc oxide.

Both the zinc salt of glycine and the zinc salt of glutamic acid are preferably used as finely pulverized powder, for example, powder having an average particle size of 10 μm or less.

The zinc salt of glycine and the zinc salt of glutamic acid can be used alone or together.

The other zinc salt used in the composition of the present invention is a basic zinc salt (C) of an organic carboxylic acid.

As such a basic zinc salt (second zinc salt (C)), a salt containing zinc in an equivalent number larger than the equivalent number of the carboxyl group of the organic carboxylic acid is preferably used.

As the organic carboxylic acid that constitutes the basic zinc salt, for example, a saturated or unsaturated monocarboxylic acid or polycarboxylic acid having 20 or less carbon atoms is preferable, and 1 carbon atom is particularly preferable.
Particularly preferred are -18 saturated monocarboxylic acids. These organic carboxylic acids may be linear or branched and may further have a substituent such as a hydroxyl group or a mercapto group.

Examples of such an organic carboxylic acid include formic acid, acetic acid,
Propionic acid, butyric acid, isobutyric acid, trimethylacetic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, tridecanoic acid, 2-ethylhexoic acid, nonanoic acid, benzoic acid,
Butylbenzoic acid, toluic acid, cinnamic acid, phenylacetic acid,
Hydroxybenzoic acid, acrylic acid, crotonic acid, acetoacetic acid, glycolic acid, lactic acid, hydroacrylic acid, propiolic acid, methacrylic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, tall oil fatty acid, versatic acid , Thioglycolic acid, mercaptopropionic acid and other monocarboxylic acids; acids, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Mention may be made of polycarboxylic acids including dicarboxylic acids such as maleic acid, azelaic acid, levulinic acid, phthalic acid, fumaric acid, malic acid.

Such a basic zinc salt can be easily produced, for example, by reacting an equivalent number of zinc oxide, which is larger than the equivalent number of the carboxyl group of the organic carboxylic acid, with the organic carboxylic acid. Zinc oxide is used in an amount of, for example, 1.01 to 4 equivalents per equivalent of the carboxyl group of the organic carboxylic acid.

In the composition of the present invention, the basic zinc salt (C) can be used alone or in combination of two or more.

Another component used in the composition of the present invention is melamine (C). Melamine (C) is preferably used as a fine powder, for example, particles having an average particle size of 10 μm or less.
By doing so, it can be dispersed uniformly in the composition.

The composition of the present invention contains at least one zinc salt selected from the group consisting of zinc salt of glycine and zinc salt of glutamic acid per 100 parts by weight of the halogen-containing resin composition (first
Zinc salt) 0.1-10 parts by weight, preferably 0.3-5.0 parts by weight,
Basic zinc salt of organic carboxylic acid (second zinc salt) 0.01-
5 parts by weight, preferably 0.1-3.0 parts by weight, and melamine
It has a weight proportion of 0.01 to 5 parts by weight, preferably 0.03 to 2.0 parts by weight.

The composition of the present invention may further contain various substances which are usually blended with the halogen-containing resin in addition to the above components. Examples of such substances include organometallic compounds, organic phosphites, antioxidants, β-diketone compounds, epoxy compounds, ultraviolet stabilizers, antistatic agents,
Surfactants, hydrotalcite compounds, polyol compounds, and their esters, organic phosphates, metal oxides, metal hydroxides, basic inorganic acid salts, perchlorates, plasticizers, pigments, fluorescent agents, A processing aid, a foaming agent, a flame retardant, etc. can be mentioned.

Further, JP-A-59-140,261 and JP-A-61-81,462.
The mixed products of hydrotalcites and perchloric acid or the acid-treated products disclosed in JP-A No. 61-83,245 can be used in combination.

Any method may be used as the method of adding the various stabilizers to the halogen-containing resin as long as the function is not impaired.

The composition of the present invention comprises the components (A), (B),
It is produced by mixing and kneading (C) and (D) together, for example, at a temperature higher than the temperature at which the halogen-containing resin melts at least. According to the research conducted by the present inventors, for example, a basic zinc salt of an organic carboxylic acid, melamine and, if necessary, an antioxidant and a lubricant in a reaction system or a pulverization system for producing a glycine zinc salt or a zinc glutamic acid salt. When a mixture of these components is once prepared and then a halogen-containing resin is mixed, the dispersion state of each component is more excellent, and the effect of the present invention is further excellently expressed. It has become clear that a composition can be provided.

<Examples> The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.

Example Common compound Polyvinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 50〃 Zinc stearate 0.5〃 Calcium stearate 0.3〃 BHP (2,6-di-t-butyl-p-cresol) 0.1〃 Diphenylmonodecyl Phosphite 0.1 〃 To the above common formulation, the substances shown in Table 1 were added and mixed thoroughly. Further, the obtained mixture was kneaded with a 6 inch × 6 inch roll heated to 170 ° C. for about 4 minutes, and then a sheet having a thickness of about 0.5 to 0.7 mm was prepared. A part of this sheet was heated to 185 ° C. in a gear aging tester and taken out every 10 minutes to observe the state of discoloration.

The degree of discoloration in the above table was judged by the following scale.

As a measure of thermal stability, the test piece was placed in a gear oven at a predetermined temperature, and the degree of discoloration after a lapse of a predetermined time was visually determined according to the following criteria.

In Table 1, the experiments of Nos. 1 and 2 are comparative examples, and Nos. 3 to 10 are examples.

Comparing Nos. 1 to 2 and 3 to 10 in Table 1, when adding amino acid zinc salt alone, or when adding melamine more than when adding two components of amino acid zinc salt and basic organic acid zinc It can be seen that is less discolored and has a longer thermal stability effect.

 The main features and aspects of the present invention are as follows.

1. (A) 100 parts by weight of halogen-containing resin (B) at least one first zinc salt selected from the group consisting of zinc salt of glycine and zinc salt of glutamic acid
0.1 to 10 parts by weight (C) At least one of basic zinc salt of organic carboxylic acid
A halogen-containing resin composition comprising an intimate mixture of 0.01 to 5 parts by weight of the second zinc salt of the seed and (D) 0.01 to 5 parts by weight of melamine.

2. The organic carboxylic acid of the second zinc salt has 1 to 20 carbon atoms
1. The composition according to 1, which is a saturated or unsaturated, mono- or di-carboxylic acid.

3. The composition according to 1 above, wherein the organic carboxylic acid of the second zinc salt is a saturated monocarboxylic acid having 1 to 18 carbon atoms.

Claims (1)

(57) [Claims] 1. A halogen-containing resin 100 parts by weight (B) At least one first zinc salt selected from the group consisting of zinc salt of glycine and zinc salt of glutamic acid.
0.1 to 10 parts by weight (C) At least one of basic zinc salt of organic carboxylic acid
A halogen-containing resin composition comprising an intimate mixture of 0.01 to 5 parts by weight of the second zinc salt of the seed and (D) 0.01 to 5 parts by weight of melamine.