JP2942942B2 - Halogen-containing resin composition with excellent 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 disadvantages of the halogen-containing resin which is unstable to heat and light, an invention using a metal silicate as a stabilizer (Japanese Patent Publication No. 52-30174) is disclosed. An invention using a metal silicate treated with an acid as a stabilizer (Japanese Patent Publication No. 4-49872) has been proposed, but 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 a calcium salt of acetylacetone, a sulfur-containing organotin compound and a calcium silicate compound were added to a halogen-containing resin.
, Magnesium silicate, aluminum silicate, silica
Selected from the group consisting of lithium silicate and barium silicate
That halogen-containing resin composition excellent in thermal stability by adding together a kind of metal silicate (or the Ke <br/> Lee acid metal salt treated with perchloric acid) as a stabilizer is obtained Heading, and led to the present invention.

[0005] The present invention is, with respect to 100 parts by weight of the halogen-containing resin, (a) calcium salt 0.01 to 5 parts by weight of acetylacetone (b) an organotin sulfur compounds 0.01 to 5 parts by weight and (c) Kay Calcium acid, magnesium silicate, silicic acid
From aluminum, lithium silicate and barium silicate
A halogen-containing resin composition having excellent thermal stability which comprises a stabilizer made of the metal silicate 0.01 to 5 parts by weight treated with selected one metal silicate or perchloric acid from the group consisting of is there.

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 copolymerization 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.

[0011] The metal silicate used in the present invention, silicic acid calcium, magnesium silicate, aluminum silicate, lithium silicate and silicic acid Barium the like <br/>.

Further, the metal silicate treated with perchloric acid used in the present invention may be prepared by mixing the metal silicate with perchloric acid or an aqueous solution of perchloric acid at room temperature or by heating the mixture. By doing so, it can be easily prepared.

The amount of perchloric acid used in the treatment is preferably in the range of 0.01 to 0.9 equivalent based on the metal oxide in the metal silicate.

Further, the halogen-containing resin composition of the present invention may contain 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.

[0015]

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

Examples 1 to 6 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Zeon Corporation), 1.0 part by weight of dioctyltin bis (isooctylmercaptoacetate), 0.5 part by weight of calcium salt of acetylacetone And a metal silicate as shown in Table 1 below were added, and the mixture 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. Was carried out, and the time until blackening was measured.

[0017]

[Table 1]

Examples 7 to 16 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Zeon Corporation) and an impact-resistant reinforcing agent (Kane Ace B-5)
2 Includes 10 parts by weight of Kanebuchi Chemical Co., Ltd., 1.0 part by weight of calcium salt of acetylacetone, 2.0 parts by weight of aluminum silicate (Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.) and organotin shown in Table 2 below. 3.0 parts by weight of the sulfur compound was added, and the same operation as in Examples 1 to 6 was performed and evaluated.

[0019]

[Table 2]

Examples 17 to 21 100 parts by weight of a post-chlorinated vinyl chloride resin (HA-15F manufactured by Tokuyama Sekisui Chemical Co., Ltd.) and an impact-resistant reinforcing agent (METABLEN C)
-150S 15 parts by weight, manufactured by Mitsubishi Rayon Co., Ltd., dioctyltin bis (isooctylmercaptoacetate) 2.0
Parts by weight, magnesium silicate (Kyoward 600, manufactured by Kyowa Chemical Industry Co., Ltd.), 1.0 part by weight, a lubricant (SL-02, manufactured by Riken Vitamin Co., Ltd.) 0.5 part by weight, and a calcium salt of acetylacetone shown in Table 3 below were added. The same operation as in Examples 1 to 6 was performed and evaluated.

[0021]

[Table 3]

Examples 22 to 24 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.) and an impact-resistant reinforcing agent (KANEACE B-3)
1 Kanebuchi Chemical Industry Co., Ltd.) 5.0 parts by weight, processing aid (METABLEN P-551A manufactured by Mitsubishi Rayon Co., Ltd.) 1.0 part by weight, calcium salt of acetylacetone 2.0 parts by weight, dioctyltin bis (isooctylmercapto) acetate)
1.0 parts by weight, 0.2 parts by weight of monobutyltin sulfide, 0.5 parts by weight of a lubricant (SL-02 manufactured by Riken Vitamin Co., Ltd.) and a metal silicate (metal silicate) treated with perchloric acid shown in Table 4 below 0.2 parts by weight of perchloric acid treated with 0.5 equivalent per 1 equivalent of the salt) was added, and the same operation as in Examples 1 to 6 was performed and evaluated.

[0023]

[Table 4]

[0024]

As is clear from the thermal stability tests of Examples 1 to 24 , calcium salts of acetylacetone, organotin sulfur compounds, calcium silicate, magnesium silicate,
Aluminum silicate, lithium silicate and barium silicate
Be added a stabilizer consisting of one selected from the group of mineral silicates (or the metal silicate treated with perchloric acid) to the halogen-containing resin comprising, highly thermally stabilize the resin effect It seems that it plays. 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.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 5:58) (56) References JP-A-57-150 (JP, A) JP-A-63-46248 (JP, A) JP 5-59237 (JP, A) JP-A-7-179702 (JP, A) JP-A-8-12834 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/04 C08K 3/34 C08K 5/07 C08K 5/58

Claims (1)

(57) [Claims] 1. A halogen containing the resin 100 parts by weight, (a) calcium salt 0.01 to 5 parts by weight of acetylacetone (b) an organotin sulfur compounds 0.01 to 5 parts by weight and (c) calcium silicate , Magnesium silicate, silicic acid
From aluminum, lithium silicate and barium silicate
Halogen-containing resin composition having excellent thermal stability which comprises a stabilizer made of the metal silicate 0.01 to 5 parts by weight treated with selected one metal silicate or perchloric acid from the group consisting of.