JP3125204B2 - Halogen-containing resin composition with improved thermal stability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to highly heat stabilized halogen containing resin compositions.

[0002]

2. Description of the Related Art Halogen-containing resins lack heat and light stability, and are liable to undergo thermal decomposition due to dehydrohalogenation during heat molding. For this reason, adverse effects such as coloring of the molded product and deterioration of mechanical properties are caused.

[0003]

In order to make up for the drawbacks of the heat- and light-unstable halogen-containing resin, an invention relating to a stabilizer using an organic tin compound and a halogen oxyacid salt in combination (Japanese Patent Publication No. 57-57056). Publication) has not yet exhibited a satisfactory stabilizing effect on heat and light.

[0004]

The inventors of the present invention have made various studies and found that the addition of a calcium salt of acetylacetone, an organotin sulfur compound, and a metal salt of perchlorate to a halogen-containing resin in combination as a stabilizer. The present inventors have found that a halogen-containing resin composition having excellent stability can be obtained, and have reached the present invention.

According to the present invention, (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) A halogen-containing resin composition having improved thermal stability, comprising a stabilizer comprising 0.001 to 5 parts by weight of a metal chlorate.

Examples of the chlorine-containing resin stabilized by the present invention include, for example, vinyl halide homopolymers such as vinyl chloride resin and vinylidene chloride resin, and vinyl halide obtained by converting vinyl halide to vinyl acetate, ethylene, propylene, styrene, isobutylene, chloride and the like. Copolymers formed by copolymerizing with one or more comonomers such as vinylidene, maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkyl maleate, post-chlorination And vinyl chloride resin. Also, 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 Polymer blend resins with impact-resistant resins such as methacrylate-acrylonitrile copolymer resins, vinyl acetate-ethylene copolymer resins, chlorinated polyethylenes, and chlorinated rubbers.

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

[0008]

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

[0009] Incidentally, in the general formula [13] - [17], specific examples of the group -OOCR ^2, such as formic acid, acetic acid, propionic acid, butyric acid, Bibarin acid, valeric acid, caprylic acid, caproic acid, decanoic acid , Lauric acid, myristic acid, palmitic acid, 2-ethylhexylic 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, coconut Oil acids, corn oil, castor oil, hardened castor oil, benzoic acid and the residues of t-butylbenzoic acid (o-, m-, p-).

Examples of the organotin sulfur compounds represented by the general formulas [1] to [19] include, for example, monomethyltin sulfide, monobutyltin sulfide, monooctyltin sulfide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dilauryl Tin sulfide, monomethyltin tris (2-ethylhexylmercaptoacetate), monomethyltin tris (isooctylmercaptoacetate), monobutyltin tris (2-ethylhexylmercaptoacetate), monobutyltin tris (isooctylmercaptoacetate), monobutyltin tris (isobutyltin) Nonylmercaptoacetate), monooctyltin tris (2-ethylhexyl mercaptoacetate), monooctyltin tris (iso Tylmercaptoacetate, monooctyltin tris (dodecylmercaptoacetate), monooctyltintris (tetradecylmercaptoacetate), monooctyltin tris (hexadecylmercaptoacetate), monooctyltin tris (octadecylmercaptoacetate), butoxycarbonyl Ethyl tin tris (2-ethylhexyl mercapto acetate), butoxycarbonylethyl tin tris (isooctyl mercapto acetate), monolauryl tin tris (2-ethylhexyl mercapto acetate), dimethyl tin bis (2-ethylhexyl mercapto acetate), dimethyl tin bis (Isooctylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyl Tin bis (isooctyl mercaptoacetate), dioctyltin bis (2-ethylhexyl mercaptoacetate),
Dioctyltin bis (isooctylmercaptoacetate), dioctyltinbis (isononylmercaptoacetate), dioctyltinbis (decylmercaptoacetate), dioctyltinbis (dodecylmercaptoacetate), dioctyltinbis (tetradecylmercaptoacetate), dioctyltin bis (hexadecyl mercaptoacetate), dioctyltin bis (octadecyl mercaptoacetate), (mercaptoacetate of C ₁₀ ~ ₁₈ mixed alcohols) dioctyltin bis,
Dilauryltin bis (2-ethylhexylmercaptoacetate), dilauryltinbis (isooctylmercaptoacetate), bis (butoxycarbonylethyl) tinbis (isooctylmercaptoacetate),
Monomethyltin tris (2-ethylhexyl mercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), monooctyltin tris (dodecylmercaptopropionate), ethoxycarbonylethyltin tris (tetradecylmercaptopropionate) ), Monolauryltin tris (isooctylmercaptopropionate), dimethyltinbis (2-ethylhexylmercaptopropionate), dimethyltinbis (isooctylmercaptopropionate), dibutyltinbis (2-ethylhexylmercaptopropionate) ), Dibutyltin bis (isooctylmercaptopropionate), dibutyltinbis (isononylmercaptopropionate), dioctyltinbis (2-ethylhexyl) Le mercaptopropionate),
Dioctyltin bis (isooctylmercaptopropionate), dioctyltinbis (isononylmercaptopropionate), dilauryltinbis (isooctylmercaptopropionate), dilauryltinbis (2
-Ethylhexylpropionate), bis (butoxycarbonylethyl) tin bis (isooctylmercaptopropionate), monomethyltin (tridecylmercaptoacetate) sulfide, monobutyltinbis (isooctylmercaptoacetate) sulfide,
Monooctyltin bis (isooctylmercaptoacetate) sulfide, monolauryltinbis (isononylmercaptoacetate) sulfide, butoxycarbonylethyltinbis (2-ethylhexylmercaptopropionate) sulfide, bis [monomethyltinbis (isooctylmercapto) Acetate)] sulfide, bis [monooctyltin bis (2-ethylhexylmercaptoacetate)] sulfide, bis [monolauryltinbis (decylmercaptoacetate)]
Sulfide, bis [dimethyltin (isooctylmercaptoacetate)] sulfide, bis [dibutyltin (isononylmercaptoacetate)] sulfide, bis [dioctyltin (2-ethylhexylmercaptoacetate)] sulfide, monobutyltin (decylmercaptopropionate) sulfide , Monolauryltin (stearylmercaptopropionate) sulfide, bis [monomethyltinbis (isooctylmercaptopropionate)] sulfide, bis [monooctyltinbis (2-ethylhexylmercaptopropionate)] sulfide, bis [dimethyltin (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-mercaptoethylcapric acid), monooctyltin tris (2-mercaptoethyl tall oil), monolauryltin tris (2
-Mercaptoethylstearic acid), butoxycarbonylethyltin tris (2-mercaptoethyloctylic acid), dimethyltinbis (2-mercaptoethyllinoleic acid), dibutyltinbis (2-mercaptoethyllaurate), dioctyltinbis (2 -Mercaptoethyl oleic acid), dilauryl tin bis (2-mercaptoethyl linolenic acid), bis (octoxycarbonylethyl) tin bis (2-mercaptoethyl cocoate), monomethyltin (2-mercaptoethyltoluate) ) Sulfide, monobutyltin (2-mercaptoethyloctylic acid) sulfide, monooctyltin bis (2-mercaptoethyltoluic acid) sulfide, bis [monomethyltin bis (2-mercaptoethyl oleic acid)] sulfide, bis Monobutyltin bis (2-mercaptoethyl soybean oil)] sulfide, bis [monooctyltin bis (2-mercaptoethyltol oil)] sulfide, bis [monolauryltin bis (2-mercaptoethyloctylic acid)] sulfide, Bis [dimethyltin (2-mercaptoethyltoluic acid)] sulfide, bis [dibutyltin (2-mercaptoethyl castor oil)] sulfide, bis [dioctyltin (2-mercaptoethylpalmitate)] sulfide, dibutyltin 3-mercaptopropio And dioctyltin mercaptoacetate.

The metal perchlorate used in the present invention includes, for example, lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, calcium perchlorate, strontium perchlorate. , Barium perchlorate, zinc perchlorate, aluminum perchlorate and the like.

For 100 parts by weight of the halogen-containing resin,
The metal perchlorate is used in combination with (a) a calcium salt of acetylacetone and (b) an organotin sulfur compound to form
Addition of 1 to 5 parts by weight can highly stabilize the halogen-containing resin.

Further, if necessary, an antioxidant, an epoxy compound,
Organic phosphites, ultraviolet absorbers, boric acid, borate esters, borates, antimony trioxide, lubricants, pigments,
Fillers, antistatic agents, flame retardants, processing aids, plasticizers and the like can be added.

[0014]

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

Examples 1 to 9 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Zeon Corporation), 1.5 parts by weight of dioctyltin bis (2-ethylhexylmercaptoacetate), 0.3 part by weight of calcium salt of acetylacetone Parts and the metal perchlorate shown in Table 1 below were added, and the mixture was mixed with a kneading roll at 190 ° C.
And kneaded for 195 minutes.
A heat stability test was conducted in an oven at a temperature of 0 ° C., and the time until blackening was measured.

[0016]

[Table 1]

Examples 10 to 19 100 parts by weight of a vinyl chloride resin (Geon 103EP-8 manufactured by Zeon Corporation) and an impact-resistant reinforcing agent (KANEACE FM)
(Kanebuchi Chemical Industry Co., Ltd.) 10 parts by weight, 1.0 part by weight of calcium salt of acetylacetone, 0.1 part by weight of barium perchlorate and 3.0 parts by weight of an organic tin sulfur compound shown in the following Table 2 were added. The same operation as in Examples 1 to 9 was performed and evaluated.

[0018]

[Table 2]

Examples 20 to 24 100 parts by weight of post-chlorinated vinyl chloride resin (HA-15F manufactured by Tokuyama Sekisui Chemical Co., Ltd.) and an impact-resistant reinforcing agent (METABLEN C)
-150S 10 parts by weight, manufactured by Mitsubishi Rayon Co., Ltd., dioctyltin bis (isooctylmercaptoacetate) 5.0
Parts by weight, 0.05 parts by weight of magnesium perchlorate, 0.5 parts by weight of a lubricant (SL-02 manufactured by Riken Vitamin Co., Ltd.) and the calcium salt of acetylacetone shown in Table 3 below were added,
The same operation as in Examples 1 to 9 was performed and evaluated.

[0020]

[Table 3]

[0021]

As is clear from the thermal stability tests of Examples 1 to 24, when a stabilizer comprising a calcium salt of acetylacetone, an organotin sulfur compound and a metal perchlorate is added to a halogen-containing resin, the resin becomes It has the effect of highly thermal stabilization. As described above, the halogen-containing resin composition of the present invention has high heat resistance and does not lower the softening temperature, and thus is suitable for heat stabilization of light, thin and short products.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-59744 (JP, A) JP-A-3-168241 (JP, A) JP-A-56-36536 (JP, A) JP-A-4- 183735 (JP, A) JP-A-1-299855 (JP, A) JP-A-62-199653 (JP, A) JP-A-5-59237 (JP, A) JP-A 8-27338 (JP, A) JP-A-53-60948 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/04-27/08

Claims (1)

(57) [Claims] (1) 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) perchloric acid based on 100 parts by weight of a halogen-containing resin. A halogen-containing resin composition having improved thermal stability, comprising a stabilizer consisting of 0.001 to 5 parts by weight of a metal salt.