JPS6231018B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized chlorine-containing resin composition, and more specifically, a stabilized chlorine-containing resin characterized in that an antimony organic sulfur-containing compound and a β-diketone metal salt compound are added together to the chlorine-containing resin. Regarding the composition. Chlorine-containing resins tend to undergo thermal decomposition mainly due to dehydrochlorination during hot molding, resulting in significant disadvantages such as deterioration of mechanical properties and color tone of processed products. Various stabilizers have been used to eliminate such disadvantages, but all of the stabilizers conventionally used had certain drawbacks and were not fully satisfactory in practice. Organic acid salts of group metals or group metals have insufficient stabilizing effects and are difficult to use alone. Furthermore, although organic tin compounds such as mono- or dialkyltin mercaptocarboxylic acid ester salts and carboxylic acid salts are extremely excellent heat stabilizers, they are insufficiently effective in preventing the initial coloring of halogen-containing resins.
Moreover, in recent years, the supply of tin has become insufficient, and organotin stabilizers have become extremely expensive. Therefore, it has been proposed to use an antimony organic sulfur-containing compound that uses inexpensive antimony, but antimony compounds are inferior in the effect of preventing coloring and have insufficient long-term thermal stabilization effects. These halogen-containing resin compositions have drawbacks such as intense discoloration when exposed to sunlight, and are extremely unsatisfactory for practical use. In order to overcome the drawbacks of antimony organic sulfur-containing compounds, it has been proposed to use various combination agents, but the effects of the combination agents proposed so far have been insufficient and unsatisfactory. For example, the combined use of an antimony organic sulfur-containing compound and soap of group A or group A metals improves long-term thermal stability, but has little effect on preventing initial coloring and thermal coloring, and does not improve light resistance. The combination of an antimony sulfur-containing compound and dibenzoylmethane improves the light resistance to some extent, but it is insufficient, and the effect of improving coloring and long-term thermal stability is small. Although the combined use of an antimony sulfur-containing compound and an organotin compound improves long-term thermal stability, the effect of improving coloration is small and light resistance is hardly improved. Although the combination of antimony sulfur-containing compounds and catechols improves initial coloration and long-term thermal stability to some extent, it is still not sufficient.
Moreover, light resistance is hardly improved. In view of the current situation, the present inventors have conducted intensive studies to obtain a stabilizer that satisfactorily improves the coloring properties, long-term thermal stability, light (climate) resistance, etc. of chlorine-containing resins. It was discovered that the coloring properties, long-term thermal stability, light (weather) resistance, etc. of chlorine-containing resins can be significantly improved by the combined addition of an antimony organic sulfur-containing compound and a metal salt of a β-diketone compound. Reached. The antimony organic sulfur-containing compound having an Sb-S group used in the present invention is, for example, Sb-(
It can be expressed as _SR1 ) ₃ . (In the formula, R ₁ is alkyl, alkenyl, aryl, -R ₂ -COOR ₃ , -R ₂ -OCOR ₃ , -R ₄ -(
Indicates COOR ₃ ) ₂ or -R ₄ - (OCOR ₃ ) ₂ . R ₂ represents alkylene or arylene, R ₃ represents alkyl, alkenyl or aryl, and R ₄ represents alkantriyl. Also, -SR ₁ is (-
SR ₂ COO―) _1/2 may be indicated. ) Also, two or more antimony atoms -SR ₂ COO-, -SR ₂ COO-R ₅ -OOCR ₂ -S-
(R ₅ represents alkylene or arylene.) Or a compound bonded with -SR ₂ OCO-R ₅ -COO-R ₂ S-, such as (R ₁ S-) ₂ Sb-SR ₂ COO-Sb- (
SR ₁ ) ₂ , (R ₁ S―) ₂ Sb―SR ₂ COO―R ₅ ―OCOR ₂ S―
Sb―(SR ₁ ) ₂ or (R ₁ S―) ₂ Sb―SR ₂ OCO―R ₅ ―
Compounds represented by COOR ₂ S—Sb—(SR ₁ ) ₂ are also useful. To explain each term in the above formulas in more detail, the alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary-butyl,
Butyl, isobutyl, pentyl, hexyl, heptyl, 1-ethylpentyl, benzyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, docosyl, triacontyl, cyclopentyl , cyclohexyl, etc., and alkenyl groups include vinyl, cyclohexyl, etc.
Examples of aryl include phenyl, naphthyl, methylphenyl, tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, etc. Alkylene includes methylene, ethylene, propylene, butylene, methylethylene, ethyl Examples include ethylene, oxydiethylene, thiodiethylene, etc. Examples of alkantriyl include 1,1,2-ethanetriyl, 1,
2,3-propanetriyl, 1,1,2-propanetriyl, 1,2,4-butanetriyl, 1,
Examples include 2,3-butanetriyl. Examples of the arylene include phenylene, naphthylene, tolylene, xylylene, and isopropylidenediphenylene. Therefore, antimony organic sulfur-containing compounds used in the present invention include, for example, Sb(SC ₈ H ₁₇ ) ₃ and Sb
(SC ₁₂ H ₂₅ ) ₃ ,

[Formula] Sb (SC ₂ H ₄ OH) ₃ ,

[Formula] Sb (SCH ₂ COO-i-C ₈ H ₁₇ ) ₃ , Sb
(SCH ₂ COOC ₁₂ H ₂₅ ) ₃ , C ₁₂ H ₂₅ S―Sb (SCH ₂ COO
―i―C ₈ H ₁₇ ) ₂ , Sb(SC ₂ H ₄ COO―i―
_C8H17 ) ₃ ,Sb _{( SCH2COO} ) _3/2 ,Sb
(SC ₂ H ₄ COO) _3/2 , Sb (SC ₂ H ₄ OOCC ₁₂ H ₂₅ ) ₃ ,
_{Sb ( SC2H4OOCC7H15 )} , Sb
_{( SC2H4OOCC17H35} ) _{3 , Sb}
(SC ₂ H ₄ OOCC ₁₇ H ₃₃ ) ₃ , [(C ₁₁ H ₂₅ COOC ₂ H ₄ S―)
₂ Sb―SC ₂ H ₄ OOCC ₂ H ₄ ―〕 ₂ , (i―
C ₈ H ₁₇ OOCCH ₂ S） ₂ SbSCH ₂ COOSb（SCH ₂ COO―
i-C ₈ H ₁₇ ) ₂ ,

【formula】

[Formula] [(i- C ₈ H ₁₇ OOCCH ₂ S) ₂ SbSCH ₂ COOCH ₂ -] ₂ ,

[Formula] Sb (SCH ₂ COOC ₂ H ₄ OOCCH ₂ SH) ₃ and the like. The β-diketone compound constituting the metal salt of the β-diketone compound used in the present invention is, for example,

It can be expressed as [Formula]. (In the formula, R ₁ and R ₂ each represent an alkyl, alkenyl or aryl group, R ₃ is a hydrogen atom,
alkyl, aryl or

[Formula] is shown. Further, R ₁ and R ₂ or R ₁ and R ₃ may be combined with each other to form a ring. ) In the above formula, examples of the alkyl group include methyl, ethyl, butyl, heptyl, isoheptyl, ethylheptyl, nonyl, decyl, undecyl, tridecyl, heptadecyl, nonadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclooctyl, benzyl, phenylethyl, etc. ,
Examples of the alkenyl group include vinyl, allyl, heptadecenyl, and cyclohexenyl, and examples of the aryl group include phenyl, naphthyl, methylphenyl, ethyl phenyl, butylphenyl, octylphenyl, and nonylphenyl.
Further, each of the above groups may be substituted with a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a carbonyl group, or the like. Examples of β-diketone compounds constituting metal salts of β-diketone compounds include benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane, bis(2-hydroxybenzoyl)methane, tribenzoylmethane, and diacetylbenzoylmethane. , stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-
methoxybenzoyl)methane, bis(4-chlorobenzoyl)methane, bis(3,4-methylenedioxybenzoyl)methane, benzoylacetyloctylmethane, benzoylacetylmethane, 2
-Hydroxybenzoylbenzoylmethane, benzoylacetylphenylmethane, stearoyl
4-methoxybenzoylmethane, bis(4-t-
butylbenzoyl)methane, benzoylacetyl ethylmethane, benzoyltrifluoroacetylmethane, diacetylmethane, butanoylacetylmethane, heptanoylacetylmethane, diacetylmethane, triacetylmethane, stearoyl acetylmethane, palmitoylacetylmethane, lauroylacetylmethane, benzoylph Enylacetylmethane, bis(cyclohexanoyl)methane, dipipaloylmethane, cyclohexane-1,
3-dione, dimedone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, acetyltetralone, benzoyltetralone, 4-methoxycarbonylbenzoylbenzoylmethane,
Examples include 12-ketostearoylbenzoylmethane. Metal components include sodium, lithium, potassium, magnesium, calcium, barium, zinc, nickel, aluminum, tin, and the like. The amount of the antimony organic sulfur-containing compound used in the present invention is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin, and the amount of the metal salt of the β-diketone compound is 0.0001 to 5 parts by weight. The amount is preferably 0.01 to 3 parts by weight. The stability and processability of the composition of the present invention can be further improved by using 0.01 to 5 parts by weight of a group A metal and/or an organic acid salt of zinc. Group A metals include calcium, magnesium, barium and strontium. Examples of the carboxylic acid constituting the metal salt of an organic acid salt that can be used in the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid,
myristic acid, palmitic acid, undecylenic acid,
Ricinoleic acid, linoleic acid, linoleic acid, neodecanoic acid, oleic acid, stearic acid, isodecanoic acid, isostearic acid. 12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, pracidic acid and similar acids, as well as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean fatty acids and Mixtures of the above naturally occurring acids such as cottonseed oil fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, pt-butylbenzoic acid,
5-t-octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid,
Examples include maleic acid, adipic acid, phthalic acid, monobutyl maleate, monodecyl phthalate, and cyclohexanecarboxylic acid. Phenols are also useful as organic acids.
For example, phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(di-
penta)isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2-
Ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octylphenol, di-t-nonyl Examples include phenol and di-t-dodecylphenol. The composition of the present invention contains 0.001 to 3 phenolic compounds.
The stability can be further improved by using parts by weight. Phenolic compounds that can be used in the present invention include 2,6-di-tert-butyl-p-cresol, catechol, tert-butylcatechol, resorcinol,
Examples include hydroquinone and 2,5-di-tert-butylhydroquinone. The composition of the present invention further contains 0.01 to 10 epoxy compounds.
By using parts by weight in combination, weather resistance, thermal stability, colorability, etc. can be improved. Epoxy compounds used in the present invention include epoxidized natural oils and fats, epoxy carboxylic acid esters, epoxidized hydrocarbons, bisphenol type or novolac type epoxy resins, etc.
Specifically, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized polybutadiene, epoxy methyl stearate, -butyl, -2-ethylhexyl, -stearyl, and tris. (Epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil butyl fatty acid, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene Diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl
Examples include 6-methylepoxycyclohexanecarboxylate. The thermal stability of the composition of the present invention can be further improved by adding 0.01 to 5 parts by weight of an organotin compound. Examples of organic tin compounds that can be used in the present invention include dibutyltin dilaurate, dibutyltin maleate, dibutyltin bis(octylmalate), dimethyltin sulfide, monobutyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, monomethyltin tris(isooctyl thioglycolate), dimethyltin bis(isooctyl thioglycolate), dimethyltin bis(mercaptoethyl laurate), dibutyltin bis(isooctyl thioglycolate), dioctyltin bis(isooctyl thioglycolate), dioctyltin bis(2-ethylhexylthioglycolate),
Examples include dibutyltin mercaptopropionate and dibutyltin isooctylthioglycolate oxide. The composition of the present invention further contains an organic phosphite compound.
0.01 to 5 parts by weight can be used together. The organic phosphite compounds that can be used in the present invention include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, tris(dinonylphenyl) ) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tris(lauryl-
2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(2'-methyl-5'-tertiary)
Butyl-4'-oxyphenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)4,
4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyl Diphenyl phosphite, tris(mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis[4-4'-n-butylidene bis(2-tert-butyl- 5-methylphenol)] thiodiethanol diphosphite, bis(octylphenyl) bis[4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite Phosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, diphenyl phosphite, tris(α
-methylbenzylphenyl) phosphite, tetratridecyl-4,4'-n-butylidene bis(2
-tert-butyl-5-methylphenol) diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyl (tridecyl) phosphite, phenyl di(tridecyl) phosphite, tris (2-cyclohexylphenyl)phosphite, ditridecyl
Di(2-cyclohexylphenyl), hydrogenated bisphenol A, diphosphite, di(2,4-di-
tert-butylphenyl) cyclohexyl phosphite, 2,4-di-tert-butylphenyl diisodecyl phosphite, tris(butoxyethoxyethyl) phosphite, diphenyloleyl phosphite, bis(2-cyclohexyl phenyl) isooctyl phosphite, bis (2,4-G-t
-butylphenyl) isooctyl phosphite. Phthalate plasticizers, polyester plasticizers, other ester plasticizers, phosphate plasticizers, chlorine plasticizers, and the like can be appropriately used in the composition of the present invention. It is also possible to add stabilizing aids commonly used in the compositions of the invention. For example, dilaurylthiodipropionate, diphenithiourea, phenyl indole, thiodiglycol bis(aminocrotonate), pentaerythritol, tris(hydroxyethyl)isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, p- Examples include t-butylbenzoic acid, dehydroacetic acid, nonylphenoxypolyethoxyphosphoric acid, benzoic acid, cinnamic acid, and dibenzoylmethane. Other materials may be added as necessary, such as pigments, fillers, plate-out inhibitors, surface treatment agents, lubricants, fluorescent agents, antifungal agents, fungicides, metal deactivators, photodegradants, infrared absorbers, processing aids, etc. Agents, mold release agents, reinforcing agents, etc. can be included. Examples of the chlorine-containing polymer used in the present invention include the following. For example, polyvinyl chloride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, 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 ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride- Isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, chloride chlorine-containing synthetic resins such as vinyl-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the above halogen-containing resins with α- Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) ), acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-
Examples include blended products with butadiene-styrene copolymer. The following examples illustrate the effects of the chlorine-containing polymer composition according to the present invention, but the present invention is not limited to these examples. Example 1 A sheet with a thickness of 1.0 mm was prepared using a kneading roll using the following formulation. This sheet was tested for thermal stability at 190°C and thermal coloring properties after 30 minutes at 190°C. Weather resistance was determined by observing the degree of discoloration after 30 days of outdoor exposure. The results are shown in Table-1. Compounded polyvinyl chloride resin 100 parts by weight Polyethylene wax 0.2 Stearyl alcohol 0.3 Calcium stearate 1.0 Antimony compound 1.0 Dibenzoylmethane-Zn 0.2 Tertiary butylcatechol 0.05

[Table] Example 2 A sheet was prepared using the following pipe formulation and tested for thermal stability at 190°C, thermal colorability after 30 minutes at 190°C, and discoloration (weather resistance) after 30 days of outdoor exposure. The results are shown in Table-2. Compounded polyvinyl chloride resin 100 parts by weight Polyethylene wax 1.0 Calcium stearate 0.8 Titanium dioxide 0.2 Carbon black 0.01 Antimony tris (2-ethylhexylthioglycolate) 0.4 parts by weight 2,6-di-tert-butyl-p-cresol
0.1 Metal salts of β-diketone compounds 0.1

【table】

[Table] Example 3 A test was conducted in the same manner as in Example 2 using the following formulation. The results are shown in Table-3. Compounded polyvinyl chloride resin 100 parts by weight Titanium dioxide 2.0 Calcium stearate 0.8 Polyethylene wax 1.0 Calcium carbonate 10 Epoxidized soybean oil 1.0 2-Hydroxybenzoylbenzoylmethane
Zn 0.5 parts by weight Antimony compound 1.0

【table】

[Table] Example 4 The same test as in Example 1 was conducted using the following profile extrusion formulation. The results are shown in Table 4. Compounded polyvinyl chloride resin 80 parts by weight ABS resin 20 Calcium carbonate 10 Calcium stearate 1.0 Paraffin wax 1.0 Stearyl alcohol 1.0 Epoxidized soybean oil 1.0 Dioctyltin bis(isooctylthioglycolate) 0.3 parts by weight Antimony tris(isooctylthioglycolate) rate) 0.3 parts by weight Metal salt of β-diketone compound 0.05

【table】

Claims (1)

[Claims] 1. Adding (a) at least one antimony mercaptide compound having a [formula] group and (b) at least one metal salt of a β-diketone compound to a chlorine-containing resin. A stabilized chlorine-containing resin composition.