JPH083400A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition excellent in thermal stability, therefore, exhibiting a high heat resistance without lowering the softening point by adding a stabilizer composed of Ca salt of acetylacetone and an organic sulfur compound to a halogen-containing resin. CONSTITUTION:This composition contains (A) 100 pts.wt. halogen-containing resin e.g. vinly chloride resin), (B) 0.01 to 5 pts.wt. Ca salt of acetylacetone and (C) 0.01 to 5 pts.wt. organic sulfur compound (e.g. monomethyltin sulfide or dioctyltin mercaptoacetate). In addition, an organotin maleate compound such as a dialkyltin maleate of the formula (R<a> is a 1 to 12C alkyl or an alkoxy- carbonylethyl; R<b> is an alkyl, an alkenl, etc.) is recommendably used in combination with the components (B) and (C) so as to improve the thermal stability and the workability of this composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a highly heat-stabilized halogen-containing resin composition.

[0002]

2. Description of the Related Art Since a halogen-containing resin lacks heat and light stability, it tends to undergo thermal decomposition due to dehydrohalogenation during heat molding. As a result, the molded product is colored, and the mechanical properties are deteriorated.

[0003]

In order to make up for the disadvantages of the halogen-containing resin which is unstable to heat and light, a combination of a metal soap and a metal salt of a diketone (Japanese Patent Publication No. 57-39260), a β-diketone is used. Combination of the above-mentioned metal salt with a zinc organic acid salt, an overbased organic sulfonate or phenate complex of an alkali or alkaline earth metal (Japanese Patent Publication No. 57-6465), a metal salt of β-diketone and hydrotal. Combined with site (Japanese Patent Publication No. 58-36012), combined use of calcium acetylacetonite with zinc organic acid salt, hydrocarbon wax, polyol ester, phosphite ester, zeolite or epoxy compound (JP-A-1). -2998
No. 55) has been proposed but has not yet exhibited a satisfactory stabilizing effect against heat and light.

[0004]

Therefore, as a result of various investigations, the present inventors have found that halogen-containing resins having excellent thermal stability can be obtained by adding a calcium salt of acetylacetone and an organic tin-containing sulfur compound to the halogen-containing resin. The inventors have found that a composition can be obtained, and completed the present invention.

In the present invention, (a) 0.01 to 5 parts by weight of a calcium salt of acetylacetone and (b) 0.01 to 5 parts by weight of an organotin-sulfur compound are added as additives to 100 parts by weight of a halogen-containing resin. It is a halogen-containing resin composition characterized by containing.

Further, if the stabilizer of the present invention comprising (a) a calcium salt of acetylacetone and (b) an organotin-sulfur compound is added together with (c) an organotin-maleic acid compound,
The heat-stabilizing effect of the halogen-containing resin can be further improved.

Examples of the chlorine-containing resin stabilized by the present invention include vinyl halide homopolymers such as vinyl chloride resin and vinylidene chloride resin, and vinyl halides such as vinyl acetate, ethylene, propylene, styrene, isobutylene, and chloride. Copolymers such as those formed by copolymerization with one or more comonomers such as vinylidene, maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkyl maleates, post chlorination Examples thereof include vinyl chloride resin. In addition, halogen-containing resins and acrylonitrile / butadiene / styrene resins, methyl methacrylate / butadiene / styrene resins, acrylonitrile / chlorinated polyethylene / styrene copolymer resins, acrylic rubber / acrylonitrile / styrene copolymers, acrylic rubber / methyl Examples thereof include a polymer blend resin with an impact resistance improving resin such as a methacrylate / acrylonitrile copolymer resin, vinyl acetate / ethylene copolymer resin, chlorinated polyethylene, and chlorinated rubber.

The organotin sulfur compound added in the present invention is
It is a compound represented by the following general formulas [1] to [19].

[0009]

Embedded image (In each formula, R is an alkyl group having 1 to 18 carbon atoms or a straight chain or branched chain, or an alkoxycarbonylethyl group having 1 to 20 carbon atoms, and R ¹ is a straight chain or branched chain having 1 to 36 carbon atoms. R ² represents a residue of a fatty acid having 1 to 22 carbon atoms or a residue of an aromatic acid, each of which has an alkyl group, an alkenyl group or an aralkyl group)

In the general formulas [13] to [17], specific examples of the group -OOCR ² include, for example, formic acid, acetic acid, propionic acid, butyric acid, bivalic acid, valeric acid, caprylic acid, caproic acid and decanoic acid. , Lauric acid, myristic acid, palmitic acid, 2-ethylhexanoic acid, stearic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, tall oil acid, soybean oil acid, cottonseed oil acid, hardened cottonseed oil acid, peanut oil acid, Residues of coconut acid, corn oil acid, castor oil acid, hardened castor oil acid, benzoic acid and t-butylbenzoic acid (o-, m-, p-) are mentioned.

Examples of the organotin-sulfur compounds represented by the general formulas [1] to [19] are, for example, monomethyltin sulfide, monobutyltin sulfide, monooctyltin sulfide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide and dilauryl. Tin sulfide, monomethyltin tris (2-ethylhexyl mercaptoacetate), monomethyltin tris (isooctyl mercaptoacetate), monobutyltin tris (2-ethylhexyl mercaptoacetate), monobutyltin tris (isooctyl mercaptoacetate), monobutyltin tris (iso) Nonylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), monooctyltin tris (isoo Tilmercaptoacetate), monooctyltin tris (dodecyl mercaptoacetate), monooctyltin tris (tetradecyl mercaptoacetate), monooctyltin tris (hexadecyl mercaptoacetate), monooctyltin tris (octadecyl mercaptoacetate), butoxycarbonyl Ethyl tin tris (2-ethylhexyl mercapto acetate), butoxycarbonyl ethyl tin tris (isooctyl mercapto acetate), monolauryl tin tris (2-ethyl hexyl mercapto acetate), dimethyl tin bis (2-ethyl hexyl mercapto acetate), dimethyl tin bis (Isooctyl mercaptoacetate), dibutyltin bis (2-ethylhexyl mercaptoacetate), dibutyl Tin bis (isooctyl mercaptoacetate), dioctyltin bis (2-ethylhexyl mercaptoacetate),
Dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (isononyl mercapto acetate), dioctyl tin bis (decyl mercapto acetate), dioctyl tin bis (dodecyl mercapto acetate), dioctyl tin bis (tetradecyl mercapto acetate), dioctyl tin bis (hexadecyl mercaptoacetate), dioctyltin bis (octadecyl mercaptoacetate), (mercaptoacetate of C ₁₀ ~ ₁₈ mixed alcohols) dioctyltin bis,
Dilauryl tin bis (2-ethylhexyl mercapto acetate), dilauryl tin bis (isooctyl mercapto acetate), bis (butoxycarbonylethyl) tin bis (isooctyl mercapto acetate),
Monomethyl tin tris (2-ethylhexyl mercapto propionate), monobutyl tin tris (isooctyl mercapto propionate), monooctyl tin tris (dodecyl mercapto propionate), ethoxycarbonyl ethyl tin tris (tetradecyl mercapto propionate) ), Monolauryl tin tris (isooctyl mercapto propionate), dimethyl tin bis (2-ethylhexyl mercapto propionate), dimethyl tin bis (isooctyl mercapto propionate), dibutyl tin bis (2-ethylhexyl mercapto propionate) ), Dibutyltin bis (isooctyl mercaptopropionate), dibutyltin bis (isononyl mercaptopropionate), dioctyltin bis (2-ethylhexyl) Le mercaptopropionate),
Dioctyl tin bis (isooctyl mercapto propionate), dioctyl tin bis (isononyl mercapto propionate), dilauryl tin bis (isooctyl mercapto propionate), dilauryl tin bis (2
-Ethylhexylpropionate), bis (butoxycarbonylethyl) tin bis (isooctylmercaptopropionate), monomethyltin (tridecylmercaptoacetate) sulfide, monobutyltin bis (isooctylmercaptoacetate) sulfide,
Monooctyl tin bis (isooctyl mercapto acetate) sulfide, monolauryl tin bis (isononyl mercapto acetate) sulfide, butoxycarbonylethyl tin bis (2-ethylhexyl mercapto propionate) sulfide, bis [monomethyl tin bis (isooctyl mercapto) Acetate)] sulfide, bis [monooctyltin bis (2-ethylhexylmercaptoacetate)] sulfide, bis [monolauryltin bis (decylmercaptoacetate)]
Sulfide, bis [dimethyltin (isooctylmercaptoacetate)] sulfide, bis [dibutyltin (isononylmercaptoacetate)] sulfide, bis [dioctyltin (2-ethylhexylmercaptoacetate)] sulfide, monobutyltin (decylmercaptopropionate) sulfide , Monolauryl tin (stearyl mercaptopropionate) sulfide, bis [monomethyl tin bis (isooctyl mercapto propionate)] sulfide, bis [monooctyl tin bis (2-ethylhexyl mercapto propionate)] sulfide, bis [dimethyl tin (Nonylmercaptopropionate)] sulfide,
Bis [dioctyltin (isooctylmercaptopropionate)] sulfide, bis [dilauryltin (isooctylmercaptopropionate)] sulfide, bis [bis (butoxycarbonylethyl) tin (isononylmercaptopropionate)] sulfide, Monomethyltin tris (2-mercaptoethyl oleic acid), monobutyltin tris (2-mercaptoethyl capric acid), monooctyltin tris (2-mercaptoethyl tall oil acid), monolauryl tin tris (2
-Mercaptoethylstearic acid), butoxycarbonylethyltin tris (2-mercaptoethyloctylic acid), dimethyltinbis (2-mercaptoethyllinoleic acid), dibutyltinbis (2-mercaptoethyllauric acid), dioctyltinbis (2 -Mercaptoethyl oleic acid), dilauryl tin bis (2-mercaptoethyl linolenic acid), bis (octoxycarbonylethyl) tin bis (2-mercaptoethyl coconut acid), monomethyltin (2-mercaptoethyl sulfonic acid) Sulfide, monobutyltin (2-mercaptoethyloctyl acid) sulfide, monooctyltin bis (2-mercaptoethyl tall oil acid) sulfide, bis [monomethyltin bis (2-mercaptoethyl oleic acid)] sulfide, bis [ Nobutyltin bis (2-mercaptoethyl soybean oil acid)] sulfide, bis [monooctyltin bis (2-mercaptoethyl tall oil acid)] sulfide, bis [monolauryltin bis (2-mercaptoethyloctyl acid)] sulfide, Bis [dimethyltin (2-mercaptoethyl tall oil acid)] sulfide, bis [dibutyltin (2-mercaptoethyl castor oil acid)] sulfide, bis [dioctyltin (2-mercaptoethyl palmitate)] sulfide, dibutyltin 3-mercaptopropio And dioctyl tin mercapto acetate.

Further, as the organotin maleic acid compound which can be added in combination with the stabilizer comprising the calcium salt of acetylacetone and the organotin sulfur compound, the dialkyltin maleate polymer represented by the general formula [A] and the general formula [A] can be used. B]
There are dialkyl tin malates represented by [C] to [C].

[0013]

Embedded image (In the formula, R ^a represents an alkyl group or an alkoxycarbonylethyl group having 1 to 12 carbon atoms, R ^b represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or a methoxybutyl group, and n represents an integer of 1 to 10. Each is shown). Examples of the R ^a group in the above formula include a methyl group, a butyl group, an octyl group, a dodecyl group, a methoxycarbonylethyl group, an ethoxycarbonylethyl group, and a butoxycarbonylethyl group, and examples of the R ^b group include an ethyl group and a butyl group. Group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, lauryl group, stearyl group, myristyl group, cetyl group, behenyl group, oleyl group, benzyl group, cyclohexyl group, methoxybutyl group, etc. You can

Furthermore, if necessary, the halogen-containing resin composition of the present invention may contain an antioxidant, an epoxy compound,
Organic phosphite, UV absorber, boric acid, borate ester, borate, antimony trioxide, lubricant, pigment,
Fillers, antistatic agents, flame retardants, processing aids, plasticizers and the like can be added.

[0015]

EXAMPLES Next, the present invention will be described with reference to examples, but parts in the examples indicate parts by weight.

Example 1 100 parts by weight of a vinyl chloride resin (Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.), 1.0 part by weight of dioctyltin bis (isooctyl mercaptoacetate) and the stabilizer shown in Table 1 below were added, The sheet was kneaded with a kneading roll at 190 ° C. for 3 minutes, and the obtained sheet having a thickness of 0.5 mm was placed in an oven at 195 ° C. to perform a thermal stability test.

[0017]

[Table 1]

Example 2 100 parts by weight of vinyl chloride resin (Geon 103EP-8, manufactured by Nippon Zeon Co., Ltd.), 1.0 part by weight of calcium salt of acetylacetone, 5 parts by weight of impact resistance enhancer (manufactured by Kaneace FM Kanegafuchi Chemical Industry Co., Ltd.), 0.5 parts by weight of a lubricant (SL-02 manufactured by Riken Vitamin Co., Ltd.) and 2.0 parts by weight of an organotin-containing sulfur compound shown in Table 2 below were added, and the same operation as in Example 1 was carried out for evaluation.

[0019]

[Table 2]

Example 3 15 parts by weight of an impact strengthening agent (Metablene C-150S manufactured by Mitsubishi Rayon Co., Ltd.) and 100 parts by weight of post-chlorinated vinyl chloride resin (HA-15F manufactured by Tokuyama Sekisui Chemical Co., Ltd.) and calcium acetylacetone. 2.0 parts by weight of salt, lubricant (S
L-02 manufactured by Riken Vitamin Co., Ltd.) 0.5 part by weight, the following third
The organotin-sulfur-containing compound and the organotin-maleic acid compound shown in the table were added, and the same operation as in Example 1 was carried out for evaluation.

[0021]

[Table 3]

[0022]

[Effect] As is clear from the thermal stability tests of Examples 1 to 3, if a stabilizer comprising a calcium salt of acetylacetone and an organic tin sulfur compound is added to the halogen-containing resin,
It can be seen that the resin is highly heat-stabilized. Furthermore, when an organotin maleic acid compound is added together with a stabilizer comprising a calcium salt of acetylacetone and an organotin sulfur compound, it becomes a practical heat stabilizer for halogen-containing resins having excellent processability. As described above, the stabilized halogen-containing resin composition according to the present invention has high heat resistance and does not lower the softening temperature, and thus is suitable for thermal stabilization of light, thin, short and small products.

Claims (2)

[Claims] 1. An additive containing (a) 0.01 to 5 parts by weight of a calcium salt of acetylacetone and (b) 0.01 to 5 parts by weight of an organotin-sulfur compound with respect to 100 parts by weight of a halogen-containing resin. A halogen-containing resin composition comprising: 2. As additives, (a) 0.01 to 5 parts by weight of a calcium salt of acetylacetone, (b) 0.01 to 5 parts by weight of an organotin-sulfur compound, and (c) to 100 parts by weight of a halogen-containing resin. )
A halogen-containing resin composition comprising 0.01 to 5 parts by weight of an organotin maleic acid compound.