JPS6412302B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized halogen-containing resin composition, and more particularly, to a stabilized halogen-containing resin composition obtained by adding an antimony mercaptide compound and a hydrotalcite compound to a halogen-containing resin. It is. Halogen-containing resins tend to undergo thermal decomposition mainly due to dehydrogenation during hot molding, resulting in deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. Maneku. In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Conventionally, various fatty acid metal salts or phenol metal salts have been used for this purpose. As a result, almost satisfactory results have been obtained in terms of heat stabilizers.
However, in recent years, these metal salts, especially cadmium salts, have serious toxicity problems and their use has been severely restricted. For this purpose, various combinations of metal salts other than cadmium salts are used, for example.
Ba/Zn series, Ca/Zn series, Ba/Ca/Zn series, etc. were proposed. However, its performance is not sufficient, and various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds,
The use of β-diketone compounds, ultraviolet absorbers, etc. has been proposed. However, even by using these in combination, the performance could not be improved to a satisfactory level. Recently, antimony mercaptide compounds have been proposed for use due to their low cost. However, this compound does not have satisfactory thermal stability, and furthermore, it has the disadvantage of being significantly colored by sunlight. Various auxiliaries have been proposed to improve these drawbacks, but these have not been sufficient to satisfy the industry. For example, when used in combination with metal soap, long-term thermal stability is improved, but light resistance is not improved at all. When used in combination with dibenzoylmethane, although some improvement in light resistance is seen, it is insufficient. When used in combination with an organic tin compound, thermal stability is sufficient, but no improvement in light resistance is observed. Further, a combination use with catechols has been proposed, but although the initial coloration property is improved, the thermal stability is insufficient and no improvement in light resistance is seen. Furthermore, the use of hydrotalcites having a specific crystal structure as a stabilizer for halogen-containing resins was proposed (Japanese Patent Laid-Open No. 80445/1983). However, hydrotalcites have a neutralizing effect as a stabilizing effect and also have a deoxidizing effect.
Since it accelerates the dehydrochlorination reaction, its use is severely limited. It also has the disadvantage of imparting color to the resin. As a result of various studies in view of the current situation, the present inventors have found that when an antimony mercaptide compound and a hydrotalcite compound are used together, the coloring property is improved.
The present invention was completed by discovering that a remarkable stabilizing effect appears on thermal stability and light resistance. That is, the present invention provides for a halogen-containing resin,
The present invention provides a stabilized halogen-containing resin composition containing an antimony mercaptide compound and a hydrotalcite compound. The composition of the present invention will be explained in detail below. The antimony mercaptide compound used in the present invention can be represented by the general formula Sb-(SR ₁ ) 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 also be indicated. ) Also, two or more antimony atoms are −SR ₂ COO−, −SR ₂ COO−R ₅ −OOCR ₂ −S−
( _R5 represents alkylene or arylene.) Or a compound bonded with _-SR2OCO - _R5 -COO- _R2S- , for example ( _R1S ) _-2Sb - _SR2COO -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−
Compounds represented by R5 _{- COOR2S} -Sb-( _SR1 ) ₂ are also useful. To explain in more detail each group represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in each of the above formulas, the alkyl groups represented by R ₁ and R ₃ include methyl, ethyl, propyl, isopropyl, Butyl, sec-butyl, tert-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., alkenyl groups include vinyl, allyl, heptadecenyl, octadecenyl, etc., and aryl groups include phenyl,
Examples include naphthyl, methylphenyl, tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, and the like. The alkylene groups represented by R ₂ and R ₅ include methylene, ethylene,
Propylene, butylene, methylethylene, ethylethylene, oxydiethylene, thiodiethylene,
Examples of the arylene group include phenylene, naphthylene, tolylene, xylylene, and isopropylidene diphenylene. _R4
The alkantriyl group represented by is 1,1,
2-ethanetriyl, 1,2,3-propanetriyl, 1,1,2-propanetriyl, 1,2,
Examples include 4-butanetriyl and 1,2,3-butanetriyl. Therefore, antimony mercaptide compounds used in the present invention include, for example, Sb(SC ₈ H ₁₇ ) ₃ ,
Sb( _SC12H25 ) _{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−C ₈ H ₁₇ ) ₃ ,
Sb (SCH ₂ COO) 3/2, Sb (SC ₂ H ₄ COO) 3/2, Sb
(SC ₂ H ₄ OOCC ₁₂ H ₂₅ ) ₃ , Sb (SC ₂ H ₄ OOCC ₇ H ₁₅ ),
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- _C8H17 ) _{2 ,}

【formula】

[Formula] [(i- C ₈ H ₁₇ OOCCH ₂ S) ₂ SbSCH ₂ COOCH ₂ ]- ₂ , Examples include Sb(SCH ₂ COOC ₂ H ₄ OOCCH ₂ SH) ₃ . The amount of the antimony mercaptide 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 halogen-containing resin. Further, the hydrotalcite compound used in the present invention is a hydrous double salt compound consisting of magnesium and aluminum and represented by the following general formula []. Mg _1-x Al _x (OH) ₂ A _x/2・mH ₂ O [] (In the above formula, x is a real number in the range of 0<x≦0.5,
A represents CO ₃ or SO ₄ and m represents a real number. ) The above hydrotalcite compound may be a natural product or a synthetic product. As a synthesis method, for example, Tokuko No. 2280, No. 1983, No. 50,
Known methods such as No. 30039 and Japanese Patent Publication No. 51-29129 can be exemplified. Furthermore, in the present invention,
It can be used without being restricted by its crystal structure or crystal particle size. The surface can also be coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acid ester, or wax. A coated material can also be used. Therefore, the amount of the hydrotalcite compound used is 0.01 parts by weight per 100 parts by weight of the halogen-containing resin.
-10 parts by weight, preferably 0.05-5 parts by weight. It goes without saying that metal organic acid salts (ordinary metal soaps) may be used in combination with the composition of the present invention. Examples of metal components in this case include Li, Na, K, Mg, Ca, Ba, Zn, Sn, Sr, etc., and organic acid residues include the following carboxylic acid and phenol residues. . Examples of carboxylic acids include acetic acid, propionic acid, butyric 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, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid, acetoxybenzoic acid , monohydric carboxylic acids such as salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, 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, thiodipropionic acid, etc. monoester or monoamide compound of divalent carboxylic acid, hemimellitic acid, trimellitic acid,
Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as merophanic acid and pyromellitic acid. Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol,
Isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol,
Examples include methylisohexylphenol and methyl-t-octylphenol. In addition, the metals (Li, Na, K, Mg, Ca,
Inorganic salts of (Ba, Zn, Sn, Sr, etc.) can also be suitably used in combination, and examples of the inorganic salts of these metals include MgO,
Oxides such as ZnO, Ca(OH) ₂ , Mg(OH) ₂ ,
Examples include hydroxides such as Ba(OH) ₂ , phosphates, phosphites, nitrates, sulfates, and the like. When the composition of the present invention is further combined with an organic phosphite compound and/or an epoxy compound, an excellent synergistic effect is exhibited. Examples of 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, and dilauryl acid. Phosphite, dibutyl acid phosphite, tris(dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite,
Bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite, 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-, di-mixed 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 (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl Diisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)
Examples include diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, and the like. The amount of these organic phosphite compounds added is
0.01 to 5 parts by weight per 100 parts by weight, preferably
It is 0.1 to 3 parts by weight. Epoxy compounds that can be used in the present invention include:
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, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil butyl fatty acid, 3-(2-xenoxy)-1 ，
Examples include 2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate. The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the resin.
Parts by weight. The polymer composition of the present invention may contain a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate plasticizer, a chlorine plasticizer, or other plasticizer depending on the purpose. Can be used as appropriate. Adding an antioxidant to the polymer composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so it can be used as appropriate depending on the purpose of use.
These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like. If an ultraviolet absorber is added to the polymer composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates,
Particularly included are nickel or chromium salts or chelates, triazine series, piverizine series, and the like. Furthermore, in order to obtain a non-toxic halogen-containing polymer, a non-toxic halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained by selecting a non-toxic one from among the commonly used metal soaps mentioned above. can get. Others as necessary, such as crosslinking agents, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifogging agents, and bactericidal agents. , metal deactivator, photodegrading agent,
Processing aids, mold release agents, reinforcing agents, etc. can be included. Examples of the halogen-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer Coalescence, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-
Maleic anhydride terpolymer, 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- Halogen-containing synthetic resins such as maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the above halogen-containing resins, polyethylene, polypropylene, polybutene, α-olefin polymers such as poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other monomers ( (e.g., maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers,
Blended products with acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, etc. can be mentioned. The following examples illustrate the effects of the halogen-containing polymer composition according to the present invention, but the present invention is not limited to these examples. Example 1 The following compound was kneaded with a roll and then pressed to produce a sheet with a thickness of 1 mm. Using this sheet, initial colorability and thermal stability at 190°C were investigated. The results obtained are shown in Table 1. <Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized linseed oil 1.0 Zinc stearate 0.3 Barium stearate 0.7 Hydrotalcite compound (Table 1)
0.1 Antimontris (2-ethylhexylthioglycolate) 0.5

[Table] Example 2 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 colorability 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 2. <Composition> Polyvinyl chloride resin 100 parts by weight Polyethylene wax 0.2 Stearyl alcohol 0.3 Calcium stearate 1.0 Antimony mercaptide compound (Table 2)
1.0 DHT-4A (Hydrotalcite compound manufactured by Kyowa Chemical Co., Ltd.) 0.1

[Table] * Thermal colorability and weather resistance are indicated by + if colored and - if not, and the number of + indicates the degree of coloring or discoloration (the same applies to Table 4).
Example 3 A sheet was made with the following formulation, and its thermal stability at 190°C, thermal colorability after 30 minutes at 190°C, and outdoor exposure were evaluated.
A discoloration (weather resistance) test was conducted after 30 days. The results are shown in Table 3. <Composition> Polyvinyl chloride resin 100 parts by weight Polyethylene wax 1.0 Calcium stearate 0.8 Titanium dioxide 0.2 Carbon black 0.01 2,6-di-tert-butyl-p-cresol
0.1 DHT-4A 0.2 Antimony mercaptide compounds (Table 3)
0.4

【table】

[Table] Example 4 A test similar to Example 2 was conducted using the following formulation. The results are shown in Table 4. <Composition> 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 Antimony tris(isooctylthioglycolate) ) 0.3 Hydrotalcite compounds (Table 4)
0.1

[Table] Example 5 In order to investigate the effect of using other stabilizing aids in combination with the composition of the present invention, a sheet was prepared in the same manner as in Example 1 using the following formulation and heated at 190°C. The thermal stability and weather resistance after 30 days of outdoor exposure were investigated. The results obtained are shown in Table 5. <Composition> 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 Antimony tris (2-ethylhexylthioglycolate) 0.2 DHT-4A 0.1 Other stabilizing aids (No. Table 5) 0.05

【table】

Claims (1)

[Claims] 1. A stabilized halogen-containing resin composition obtained by adding an antimony mercaptide compound and a hydrotalcite compound to a halogen-containing resin.