JP2535049B2 - Chlorine-containing synthetic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a stabilized chlorine-containing synthetic resin composition. More specifically, the present invention relates to a chlorine-containing synthetic resin composition in which choking is prevented and thermal stability and colorability are improved by adding a copper-containing phosphorus compound to a chlorine-containing synthetic resin.

[Problems to be Solved by Prior Art and Invention]

Generally, chlorine-containing synthetic resins are inferior in stability to heat and light and are liable to undergo thermal decomposition mainly due to dehydrochlorination during heat molding processing, which results in deterioration of mechanical properties and deterioration of color tone of processed products. It causes serious disadvantages.

Conventionally, in order to improve such drawbacks, one or several kinds of stabilizers have been added and stabilized.

Among these stabilizers, lead-based stabilizers are widely used because they have a relatively large thermal stability effect.

However, the halogen-containing synthetic resin to which the lead-based stabilizer is added has a drawback that it causes coloring during processing, has insufficient weather resistance, and causes a whitening phenomenon called chalking especially when it is used outdoors. Therefore, various attempts have conventionally been proposed to meet these requirements.

For example, addition of a copper salt of an organic carboxylic acid (JP-A-59-10)
2943), addition of a metal salt of thiocyanic acid (see JP-A-59-64652), etc., but none of them were able to obtain a sufficiently satisfactory effect, and further improvement was demanded. .

Further, recently, higher thermal stability under severe temperature conditions is required.

[Means for solving the problem]

The present inventors, in view of these circumstances, as a result of repeated earnest studies, by adding a copper-containing phosphorus compound, choking is prevented, moreover, thermal stability, thermal colorability and initial colorability are significantly improved. It has been found that a chlorine-containing synthetic resin composition can be obtained.

The present invention has been made on the basis of the above-mentioned findings, and is based on the following general formulas (I), (II) and (III)
The present invention provides a stabilized chlorine-containing synthetic resin composition obtained by adding at least one compound selected from the compound group represented by:

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group or an ether-containing alkyl group, and n ₁ , n ₂ , n ₃ and n ₄ each independently represents 0 or 1.) The chlorine-containing synthetic resin composition of the present invention having the above characteristics will be described in detail below.

Representative examples of the copper-containing phosphorus compounds represented by the general formulas (I), (II) and (III) include the compounds shown in Table 1 below.

The addition amount of the copper-containing phosphorus compound represented by the general formulas (I), (II) and (III) is 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing synthetic resin. Is preferred.

Examples of the chlorine-containing synthetic resin used in the present invention include the following. For example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, 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 copolymer, vinyl chloride-butadiene copolymer Polymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleic acid Ester copolymer, vinyl chloride-methacrylic acid ester copolymer, salt Vinyl-acrylonitrile copolymer, chlorine-containing synthetic resin such as internally plasticized polyvinyl chloride, and higher chlorine-containing synthetic resin, and α-olefin polymer such as polyethylene, polypropylene, polybutene, poly-3-methylbute or ethylene-acetic acid. Vinyl copolymers, polyolefins such as ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resins, copolymers of styrene and other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), Acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-
Examples thereof include blended products with a styrene copolymer.

Needless to say, conventionally used inorganic and organic lead-based stabilizers, organic acid metal salts, and organic tin compounds can be used in combination in the composition of the present invention.

Examples of these lead-based stabilizers include lead white, chlorinated lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, Silica gel co-precipitated lead silicate, dibasic lead phthalate, tribasic lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate, 12
-Lead hydroxystearate, lead octylate, lead behenate, lead naphthenate and the like.

Further, as the metal component of the organic acid metal salt that can be used in combination with the composition of the present invention, LiSK, Na, Mg, Sr, Ca, Ba, Zn, Cd, Sn, P
h, Sb, etc., the following carboxylic acids as organic acid residues,
Examples thereof include residues of phenols, organic phosphoric acid or phosphorous acid, and mercaptans.

Examples of the carboxylic acid include acetic acid, propionic acid,
Acetic acid, valeric acid, caproic acid, enanthic acid, caprylic acid,
Neodecanoic acid, 2-ethylhexylic acid, pelargonic acid,
Capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid,
Stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-
Tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3.
5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n
-Propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p
-Tertiary octyl salicylic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, monovalent carboxylic acid such as octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid , Aconitic acid,
Divalent carboxylic acids such as thiodipropioic acid or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid,
Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as trimellitic acid, melophanoic acid and pyromellitic acid.

Further, examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n.
-Butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadicylphenol, diisobutylphenol, methylpropylphenol, diamylphenol , Methylisohexylphenol, methyl tertiary octylphenol and the like.

Examples of organic phosphoric acid or phosphorous acid include mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl. , -Nonylphenylphosphoric acid-pyrophosphoric acid or phosphorous acid.

Examples of mercaptans include octyl mercaptan, dodecyl mercaptan, octadecyl mercaptan, isooctyl mercapto acetate, 2-ethylhexyl mercapto acetate, dodecyl mercapto acetate, tetradecyl mercapto acetate, isooctyl mercapto propionate, and mercapto ethyl oleate.

The organotin compounds that can be used in combination with the composition of the present invention include the following organotin mercaptides (1) to (5), organotin sulfides, organotin mercaptide / sulfides, organotin mercaptocarboxylates. And organotin carboxylates.

(1) Organic tin mercaptides include dibutyltin bis (lauryl mercaptide), dimethyltin bis (stearyl mercaptide), dioctyltin bis (mercaptoethyl tall oil fatty acid ester), dioctyltin bis (2-mercapto). Ethyl caprylate), dibutyltin bis (mercaptoethyl tall oil fatty acid ester),
Dimethyltin bis (mercaptoethyl stearate), dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexylthioglycolate), dioctyltin bis (dodecylthioglycolate), dioctaltin bis (tetradecylthio) Glycolate), dioctyl tin bis (hexadecyl thioglycolate), dioctyl tin bis (octadecyl thioglycolate), dioctyl tin bis (C _12-16 mixed alkyl thioglycolate), dibutyl tin bis (isooctyl thioglycolate), Diorganic compounds such as dimethyltin bis (isooctyl mercaptopropionate), bis (2-mercaptocarbonylethyl) tin bis (isooctylthioglycolate), bis (2-butoxycarbonylethyl) tin bis (butylthioglycolate) tin Mercaptide and monobutyltin tris (lauryl mercaptide), monobutyl monochlorotin bis (lauryl mercaptide), monooctyltin tris (2-mercaptoethyl caprylate), monobutyltin tris (mercaptoethyl tall oil fatty acid ester) , Monomethyltin tris (mercaptoethyl tall oil fatty acid ester), monomethyltin tris (mercaptoethyl laurate), monomethyltin tris (mercaptoethyl stearate), monomethyltin tris (mercaptoethyloleate), monooctyltin tris (isooctyl) Thioglycolate), monooctyltin tris (2-ethylhexyl thioglycolate), monooctyltin tris (dodecyl thioglycolate), monooctyl tin triu (dodecyl thioglycolate) Monooctyltintris (tetradecyl thioglycolate), monooctyltin tris (hexadecyl glycolate), monooctyltintris (C _12-16 mixed alkyl thioglycolate), monooctyltin tris (octadecyl thioglycolate), monobutyltin Tin tris (isooctyl thioglycolate), monobutyl tin tris (isooctyl mercaptopropionate), monomethyl tin tris (isooctyl thioglycolate), monomethyl tin tris (tetradecyl thioglycolate), 2-methoxycarbonylethyl tin Examples include monoorganotin mercaptides such as tris (isooctylthioglycolate) and 2-butoxycarbonylethyltin tris (2-ethylhexylthioglycolate).

(2) Examples of organic tin sulfides include methylthiostannoic acid, butylthiostannoic acid, octylthiostannoic acid, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dicyclohexyltin sulfide, monobutyltin sulfide. Oxide, 2-methoxycarbonylethyltin sulfide, 2-ethoxycarbonyltin sulfide, 2-butoxycarbonylethyltin sulfide, 2-isopropoxycarbonylethyltin sulfide, bis (2-methoxycarbonylethyl) tin sulfide, bis (2-propoxy Carbonylethyl) tin sulfide and the like.

(3) As the organic tin mercaptide sulfides, bis [monobutyl di (isooctoxycarbonylmethylenethio) tin] sulfide, bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, bis [bis (2- Methoxycarbonylethyl)
Tin isooctyl thioglycolate] sulfide, bis (methyltin diisooctyl thioglycolate) disulfide, bis (methyl / dimethyl tin mono / diisooctyl thioglycolate) disulfide, bis (methyl tin diisooctyl thioglycol) Rate) Trisulfide,
Bis (butyltin diisooctylthioglycolate) trisulfide, bis [methyltin di (2-mercaptoethylcaprylate) sulfide, bis [methyltin di (2
-Mercaptoethyl caprylate)] disulfide and the like.

(4) As the organic tin mercaptocarboxylates,
Dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, bis (2-methoxycarbonylethyl) tin thioglycolate, bis (2-methoxycarbonylethyl) tin mercaptopropionate Nate, etc.

(5) Examples of the organic tin carboxylates include mono- or dimethyl tin, mono- or dibutyl tin, mono- or di-octyl tin, or mono- or bis (ptoxycarbonylethyl) tin octoate, laurate, myristate, palmitate, stearate, iso- Examples thereof include aliphatic monovalent carboxylates such as stearates; malates such as malate polymers, butyl maleates, benzyl malates, oleyl malates and stearyl malates; and mixed salts or basic salts thereof.

The composition of the present invention further comprises, if necessary, an epoxy compound, DOP, a plasticizer such as polyester, a phenolic antioxidant such as BHT, an organic phosphorus compound such as trisnonyl phosphite, and a sulfur antioxidant such as DSTDP. Agents, benzophenone-based, benzotriazole-based or hindered amine-based light stabilizers, anti-plateout agents, antifog agents, fluorescent agents, antifungal agents, bactericides, surface treatment agents, metal deactivators, photodegradants, release agents A mold agent, a reinforcing agent, a crosslinking agent, a pigment, a paint, a filler, carbon black, a foaming agent, a processing aid, a lubricant, an antistatic agent, a flame retardant and the like can be included.

〔Example〕

The following examples show the effects of the chlorine-containing synthetic resin composition of the present invention, but the present invention is not limited to these examples.

Example 1 The following formulation was roll kneaded at 190 ° C. for 5 minutes and then 170
The sample was pressed at 200 ° C. and 200 kg / cm ² for 5 minutes to prepare a 1 mm-thick test piece. Put this sample in an oven at 175 ° C,
A thermal stability test was performed and the time until blackening was measured.
In addition, an outdoor exposure test was performed to measure the period until whitening (chalking). The results are shown in Table 2 below.

(Combination) Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Calcium carbonate 2 Calcium stearate 0.3 Gray pigment 0.2 Tribasic lead sulfate 0.5 Dibasic lead stearate 0.3 Lead stearate 1.5 Reagents (Table-2) * * Uses 0.3 parts by weight of copper stearate plus metal content.

Example 2 A test piece was prepared in the same manner as in Example 1 using the following formulation, and its performance test was conducted. The results are shown in Table 3 below.

(Combination) Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Calcium carbonate 2 Calcium stearate 1.0 Gray pigment 0.2 Dibutyltin bis (octylthioglycolate) 2.0 Oxidized polyethylene wax 0.3 Paraffin wax 0.8 Reagents (Table-3) * * Uses 0.3 parts by weight of copper stearate plus metal content.

Example 3 A test piece was prepared in the same manner as in Example 1 using the following formulation, and its performance test was conducted. The results are shown in Table 4 below.

(Combination) Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Calcium carbonate 7 Gray pigment 0.2 Zinc stearate 2.4 Calcium stearate 1.2 Dipentaerythritol 1.0 Sample (Table 4) ** Metal content in 0.3 parts by weight of copper stearate Use the combined amount.

[Effects of the Invention] The chlorine-containing synthetic resin composition of the present invention is one in which chalking is prevented and, in addition, thermal stability, thermal colorability and initial colorability are remarkably improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-58-21438 (JP, A) JP-A-54-95651 (JP, A) JP-A-58-101138 (JP, A) JP-A-54- 102348 (JP, A)

Claims (1)

(57) [Claims] 1. A chlorine-containing synthetic resin having the following general formula (I):
A stabilized chlorine-containing synthetic resin composition obtained by adding at least one compound selected from the group of compounds represented by (II) and (III). (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group or an ether-containing alkyl group, and n ₁ , n ₂ , n ₃ and n ₄ independently represents 0 or 1.)