JPH052700B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to a stabilized halogen-containing resin composition, specifically, a method in which a specific antimony organic sulfur-containing compound (antimony mercapto compound) and a specific epoxy compound are added together to a halogen-containing resin. The present invention relates to a stabilized halogen-containing resin composition characterized by the following. [Problems to be solved by the prior art and the invention] Halogen-containing resins tend to undergo thermal decomposition mainly due to dehydrohalogenation during thermoforming processing, which leads to deterioration of the mechanical properties of processed products. The color tone deteriorates, resulting in significant disadvantages. 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. For example, organic acid salts of group metals or group metals have insufficient stabilizing effects and are difficult to use alone. Furthermore, organic tin compounds such as mono- or dialkyltin mercaptocarboxylic acid ester salts and carboxylic acid salts are extremely excellent heat stabilizers;
The effect of preventing the initial coloring of halogen-containing resins is insufficient, and furthermore, the supply of tin has been insufficient in recent years, making them 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. The halogen-containing resin composition containing the above has drawbacks such as intense discoloration when exposed to sunlight, and is extremely unsatisfactory for practical use. The use of various combination agents has been proposed to overcome the drawbacks of antimony organic sulfur-containing compounds, but all of the combination agents proposed so far have been unsatisfactory as their effects have been insufficient. For example, antimony organic sulfur-containing compounds and group a or a
The combined use of group metal soaps improves long-term thermal stability, but has little effect on preventing initial discoloration and thermal discoloration, and also does not improve light fastness. Although the combined use of an antimony sulfur-containing compound and dibenzoylmethane improves light resistance to some extent, it is insufficient, and the effect of improving coloring and long-term thermal stability is small. The combined use of an antimony sulfur-containing compound and an organotin compound improves long-term thermal stability, but the effect of improving coloration is small and hardly improves light resistance. The combined use of antimony sulfur-containing compounds and catechols improves initial coloration and long-term thermal stability to some extent, but it is still not sufficient and hardly improves light resistance. Therefore, an object of the present invention is to provide a stabilizer that improves the colorability, long-term thermal stability, light resistance, etc. of halogen-containing resins to a sufficiently satisfactory degree. [Means for Solving the Problems] As a result of extensive studies, the present inventors have found that the above objective can be achieved by using a specific antimony organic sulfur-containing compound and a specific epoxy compound together with a halogen-containing resin. The inventors have discovered that the following can be achieved, and have arrived at the present invention. That is, the halogen-containing resin composition of the present invention includes (1) at least one antimony mercapto compound represented by the following general formula () and
(2) At least one type of epoxy compound represented by the following general formula () or a polymer of glycidyl acrylate or glycidyl methacrylate is added. Sb(−S−R ₁ ) ₃ () (In the formula, R ₁ represents an alkyl group, an alkenyl group, a phenyl group, -R ₂ -COOR ₃ or -R ₂ -OCOR ₃ ,
R ₂ represents a methylene group or an ethylene group, R ₃ represents an alkyl group, R ₄ represents a residue obtained by removing one or two carboxyl groups from a monovalent or divalent carboxylic acid, and n is 1 or 2 shows. ) Hereinafter, the halogen-containing resin composition of the present invention will be explained in detail. In the above general formula (), the alkyl groups represented by R ₁ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, benzyl, octyl, isooctyl, 2
- Examples of the alkenyl group represented by _R1 include vinyl, allyl, hexenyl, octenyl, and oleyl. etc. can be mentioned. Therefore, the antimony organic sulfur-containing compound (antimony mercapto compound) used in the present invention includes, for example, Sb(SC ₈ H ₁₇ ) ₃ , Sb(SC ₁₂ H ₂₅ ) ₃ , Sb(SC ₆ H ₅ ) ₃ , Sb
(SCH ₂ COO−i−C ₈ H ₁₇ ) ₃ , Sb
(SCH ₂ COOCH ₁₂ H ₂₅ ) ₃ , Sb (SCH ₂ COOCH ₂ CH
( _C2H5 ) _C4H9 ) ₃ , _Sb ( _{SC2H4COO -} i _{- C8H17} ) _{3 ,}
Sb _{( SC2H4OOCC11H23 ) 3 ,} Sb
(SC ₂ H ₄ OOCC ₇ H ₁₅ ) ₃ , Sb (SC ₂ H ₄ OOCC ₁₇ H ₃₅ ) ₃ ,
Examples include Sb (SC ₂ H ₄ OOCC ₁₇ H ₃₃ ) ₃ . Further, examples of the carboxylic acid constituting the carboxylic acid residue represented by R ₄ of the epoxy compound represented by the general formula () include acetic acid, propionic acid, caproic acid, caprylic acid, undecanoic acid, lauric acid, Saturated monovalent fatty acids such as myristic acid, palmitic acid, decanoic acid, neodecanoic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, behenic acid, versatic acid; acrylic acid, methacrylic acid, crotonic acid, Linderic acid,
Unsaturated monovalent fatty acids such as oleic acid, linoleic acid, and linoleic acid; Saturated divalent fatty acids such as oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid, and sebacic acid; Unsaturated divalent fatty acids such as maleic acid, fumaric acid, etc. Carbocyclic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, benzoic acid; From vegetable oils such as coconut oil, soybean oil, safflower oil, and linseed oil Examples include mixtures of fatty acids obtained. Further, the polymer of glycidyl acrylate or glycidyl methacrylate (epoxy compound) used in the present invention may be a homopolymer thereof or a copolymer with other monomers. These monomers include acrylic acid, methacrylic acid, and methyl, ethyl,
Examples include n-butyl, isobutyl, t-butyl, cyclohexyl, 2-ethylhexyl, dodecyl, pentadecyl, hexadecyl, octadecyl esters, styrene, α-methylstyrene, acrylonitrile, etc. The ratio in the case of copolymerization is selected so that the epoxy compound accounts for 15% by weight or more, preferably 30% by weight or more. Therefore, examples of the epoxy compound (2) used in the present invention include glycidyl laurate, glycidyl stearate, β-methylglycidyl stearate, glycidyl isostearate, glycidyl versatate, glycidyl acrylate, and glycidyl methacrylate. , β-methylglycidyl methacrylate and homopolymers of these acrylates or these acrylates and methyl methacrylate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate,
or copolymers with acrylonitrile, glycidyl oleate, glycidyl linoleate, diglycidyl adipate, diglycidyl azelate, diglycidyl maleate, diglycidyl phthalate, bis(β-methylglycidyl) phthalate, diglycidyl isophthalate, diglycidyl hexahydrophthalate , diglycidyl tetrahydrophthalate, dimer acid diglycidyl ester, glycidyl benzoate, coconut oil fatty acid glycidyl ester, soybean oil fatty acid glycidyl ester, and the like. In the present invention, the amount of the antimony organic sulfur-containing compound (antimony mercapto compound) added is 0.01 to 10 parts by weight per 100 parts by weight of the halogen-containing resin.
Parts by weight, particularly preferably 0.1 to 5 parts by weight,
The amount of the epoxy compound added is 0.01 to 10 parts by weight, especially
The amount is preferably 0.1 to 5 parts by weight. The stability and processability of the composition of the present invention can be further optimized by using 0.01 to 5 parts by weight of a group A metal and/or zinc organic acid salt. Group A metals include calcium, magnesium, barium and strontium. Examples of carboxylic acids constituting the metal salt of an organic acid salt that can be used in the present invention include caproic acid, pelargonic acid, uraric acid, 2-ethylhexylic acid,
myrictic 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, behenyl acids, erucic acid, pracidic acid and similar acids and naturally occurring mixtures of the above acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and 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,
Examples include di-t-butylbenzoic acid, bromobenzoic acid, maleic acid, adipic acid, phthalic acid, monobutyl maleate, monodecyl phthalate, and cyclohexanecarboxylic acid. Phenols are also useful as organic acids. Examples of such phenols include phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, and tetramethylphenol. , poly(di-penta)isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2-ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octyl Phenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol,
Examples include methyl-t-octylphenol, di-t-nonylphenol, di-t-dodecylphenol, and the like. The composition of the present invention contains phenolic compounds from 0.001 to
The stability can be further improved by using 3 parts by weight. Phenolic compounds that can be used in the present invention include 2,6-di-tert-butyl-p-cresol,
Examples include catechol, tert-butylcatechol, resorcinol, hydroquinone, 2,5-di-tert-butylhydroquinone, and the like. 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, dibutyltin isooctylthioglycolate oxide, and the like. The composition of the present invention may further contain 0.01 to 5 parts by weight of an organic phosphite compound. Organic phosphite compounds that can be used in the present invention include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (mono-, di-mixed nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, -cyclohexyl phenyl) phosphite, diphenyldecyl phosphite, diphenyl octyl phosphite, diphenyl(tridecyl) phosphite, bis(2,4-di-tert-butylphenyl)cyclohexyl phosphite, bis(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) phosphite, 3-butylphenyl) isooctyl phosphite, bis(2-cyclohexyl phenyl) isooctyl phosphite, diphenyloleyl phosphite, phenyl di(tridecyl) phosphite, 2,4-di-tert-butylphenyl diisodecyl phosphite, tridecyl phosphite phosphite, tridodecyl phosphite, tris(butoxyethoxyethyl) phosphite,
Bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,
Phenyl/4,4'-isopropylidene diphenol/pentaerythritol diphosphite, tetra( _C12-15 mixed alkyl)/4,4'-isopropylidene diphenyl diphosphite, hydrogenated- ₄ ,
Examples thereof include 4'-isopropylidene diphenol polyphosphite, di(tridecyl) bis(2-cyclohexyl phenyl) and hydrogenated 4,4'-isopropylidene diphenyl diphosphite. 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, diphenylthiourea,
Phenylindole, thiodiglycol bis(aminocrotonate), pentaerythritol, tris(hydroxyethyl)isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, pt-butylbenzoic acid, dehydroacetic acid, nonylphenoxylate Cypolyethoxyphosphoric acid,
Examples include benzoic acid, cinnamic acid, and dibenzoylmentha. If necessary, the composition of the present invention may include pigments, fillers, plate-out inhibitors, surface treatment agents, lubricants, fluorescent agents, fungicides, bactericidal agents, metal deactivators, photodegradants, etc. , an infrared absorber, a processing aid, a mold release agent, a reinforcing agent, and the like. Examples of the halogen-containing polymer used in the present invention include 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, 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-maleic acid ester copolymer, chloride Halogen-containing resins such as vinyl-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene,
α-olefin polymers such as poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof, polystyrene, acrylic resins,
Styrene and other monomers (e.g. maleic anhydride,
butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, etc. can. 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 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 (see Table 1) 1.0 Glycidyl methacrylate/methyl methacrylate copolymer (GX-50 manufactured by NOF Corporation) 0.2 3-butylcatechol 0.05

[Table] Example 2 A sheet was made using the following pipe composition and heated to 190°C.
Thermal stability at 190°C for 30 minutes, and color change (weather resistance) after 30 days of outdoor exposure were tested. 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 2,6-di-tert-butyl-p-cresol 0.1 Epoxy compound ( (See Table-2) 0.1

[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 Glycidyl methacrylate 1.0 Antimony compound (see Table 3) 1.0

[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 MBS resin 20 Calcium carbonate 10 Calcium stearate 1.0 Paraffin wax 1.0 Stearyl alcohol 1.0 Epoxy compound (see Table 4) 1.0 Dioctyltin bis (isooctyl thioglycolate) 0.5 Antimony tris (isooctyl Thioglycolate) 0.5

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Claims (1)

[Scope of Claims] 1 A halogen-containing resin containing (1) at least one antimony mercapto compound represented by the following general formula () and (2) an epoxy compound or glycidyl acrylate represented by the following general formula () Alternatively, a stabilized halogen-containing resin composition containing at least one type of glycidyl methacrylate polymer. Sb(−S−R ₁ ) ₃ () (In the formula, R ₁ represents an alkyl group, an alkenyl group, a phenyl group, -R ₂ -COOR ₃ or -R ₂ -OCOR ₃ ,
R ₂ represents a methylene group or an ethylene group, R ₃ represents an alkyl group, R ₄ represents a residue obtained by removing one or two carboxyl groups from a monovalent or divalent carboxylic acid, and n is 1 or 2 shows. )