JPS6148539B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyvinyl chloride resin stabilizing composition. More specifically, the present invention relates to a halogen-containing resin stabilized composition that has excellent coloring resistance and is improved in heat resistance, weather resistance, roll surface sticking phenomenon (plate-out phenomenon), and additive blow-out phenomenon (blooming phenomenon). It is well known that polyvinyl chloride resins become colored due to heating during molding or photodeterioration, mainly caused by ultraviolet rays, after they are made into processed products, making it impossible to produce excellent products. In order to improve these drawbacks, various stabilizers have been proposed and put into practical use. As is well known, the performance required of stabilizers for polyvinyl chloride resins is wide-ranging in addition to the above-mentioned heat and light performance. Conventionally used stabilizers have various characteristics as their effects,
A fully satisfactory stabilizer has not yet been obtained. Even though relatively excellent stabilizers have been put into practical use, stabilizers with even better effects are required in order to obtain even better products. For example, organotin stabilizers have very good effects. In particular, organic tin mercapto stabilizers are very effective stabilizers with excellent heat resistance and initial coloring effects, but they have strong peculiar odors and still pose problems in the working environment. Furthermore, organic acid salts of alkaline earth metals generally have excellent heat resistance, but are poor in initial coloring properties. For this reason, for example, when obtaining a colored product, it not only takes time to delicately match the colors, but also changes due to processing temperature and time, making it difficult to obtain the desired uniform colored product. There is. Therefore, in order to supplement this, an organic acid salt of zinc was added to obtain the desired initial coloration, and the thermal stability,
Transparency decreases, giving rise to concerns about thermal processing. As a result of various studies conducted by the present inventors, (1) 1,1,3-tris[(2'-methyl-4'-di-tridecylphosphite-5-tert-butyl)phenyl was added to polyvinyl chloride resin. ]
Butane (hereinafter referred to as No. 1 compound), trisnonylphenyl phosphite (hereinafter referred to as No. 2 compound) and/or 4,4'-isopropylidene diphenolalkyl (C ₁₂ - C ₁₅ ) phosphite (hereinafter referred to as No. 3) 1. A polyvinyl chloride resin stabilizing composition, characterized in that it has a polyvinyl chloride resin stabilizer. (2) A polyvinyl chloride resin composition, characterized in that diphenyl phosphite (hereinafter referred to as No. 4 compound) is further added to the above composition. By doing so, as specifically shown in the examples, it has extremely excellent coloring resistance and weather resistance, as well as heat resistance,
The inventors have discovered that blooming and plate-out phenomena are significantly improved, leading to the present invention. The three types of compounds used in the above (1) are known as stabilizers for polyvinyl chloride resins. However, when these are used alone, a sufficient stabilizing effect cannot be expected as shown in the comparison of Examples below. However, according to the present invention,
Mainly No.1 compound, No.1 compound and No.2 compound, No.1 compound and No.3 compound, No.1 compound
It was discovered that when used in combination of No. 2 compound and No. 3 compound, that is, a selective combination of specific phosphites, an unexpected synergistic effect is surprisingly exhibited, leading to the present invention. It is. As a result of further research, the present inventor found that by adding Compound No. 4 to each of these compositions in combination, the stabilizing effect could be further promoted, and the second invention was completed. In the present invention, each of the above four types of phosphites is used in a proportion of 0.005 to 5 parts by weight, and a total of 0.1 to 5 parts by weight, per 100 parts by weight of the polyvinyl chloride resin. The polyvinyl chloride resin to be stabilized in the present invention includes polyvinyl chloride and vinyl chloride as main components, copolymers with monomers that can be copolymerized with the polyvinyl chloride, graft polymers, block polymers, and polymers containing these. The main component is a polymer blend. One or more other commonly used stabilizers or additives may be added to the stabilized composition of the present invention. These include, for example, plasticizers, organic phosphites other than those of the present invention, organic phosphate esters, organic tin compounds, organic or inorganic antimony compounds, organic or inorganic titanium compounds, metal soaps, epoxy compounds, ultraviolet absorbers, and antioxidants. agents, viscosity modifiers, pigments, dyes, processing aids, impact reinforcement agents, mold release agents, surface treatment agents, antibacterial agents, fluorescent whitening agents, antifogging agents, non-dripping agents, dripping agents, Antistatic agents, polyhydric or higher alcohols, saturated and unsaturated fatty acids with linear or side chains, other organic solvents, lubricants, fillers, flame retardants, fragrances, organic compounds or their salts, crosslinking agents plate-out prevention agents, etc. Specific examples of organic phosphites other than those of the present invention include triphenyl phosphite, tricresyl phosphite, triisooctyl phosphite,
Tridecyl phosphite, tri-2-ethylhexyl phosphite, tridecyl phosphite, tri(octylphenyl) phosphite, tricyclohexyl phenyl phosphite, triscyclohexyl phosphite, tridecylthiophosphite, triisodecylthiophosphite , phenyl di-2ethylhexyl phosphite, phenyl diisodecyl phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di(tridecyl) phosphite, phenyl dicyclohexyl phosphite, diphenyl Isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl tridecyl thiophosphite, nonylphenyl di(tridecyl) phosphite, phenyl p-tertiary Butyl dodecyl phosphite, diisopropyl phosphite, monoisopropyl phosphite, diisodecyl phosphite, diisooctyl phosphite,
Monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, dicyclohexyl phenyl phosphite, monodicyclohexyl phenyl phosphite, di(p-tertiarybutyl phenyl) phosphite, Tetra(tridecyl)-4,4'-butylidenebis(2-tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl [4,4'-thiobis(2-tert-butyl-5-methylphenol)] diphosphite, tetra Nonylphenyl polypropylene glycol
Diphosphite, tetra(tridecyl)dipropylene glycol diphosphite, tetratridecyl-4,4'-isopropylidenecyclohexyl diphosphite, pentakis(nonylphenyl)bispolypropylene glycol triphosphite,
heptakis (nonylphenyl) tetrakis polypropylene glycol pentaphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, decakis (nonylphenyl) heptakis (dipropylene glycol) octaphosphite, decaphenyl heptadipropylene glycol octaphosphite, Tetrakis (isooctoxycarbomethylenethio)
1,2-oxycarbonylmethylenethioethylene diphosphite, dibutoxycarboethylenethio (pentaerythritol tetrathioglycol)
Diphosphite, diisooctoxycarbomethylenethio (pentaerythritol tetrathioglycol) diphosphite, tetrakis (mercaptrauryl) 1,2-dimercapto-ethylene diphosphite, tetrakis (mercaptrauryl)
1,6-dimercapto-hexylene diphosphite, tetrakis (mercaptrauryl) β, β'
-dimercapto-ethyl ether diphosphite, pentakis(dodecyl-mercapto)bis(1,6-hexylene dimercapto)triphosphite, tris(2,4-di-tertiarybutylphenyl)phosphite, 4,4'- Butylidene-bis(3-methyl-6-tert-butylphenyl-di-dodecyl) phosphite, hydrogenated 4,
4'-isopropylidene diphenol phosphite, 2-tert-butyl-α (3-tert-butyl-4-hydroxyphenyl) p-cumenylbis(p-nonylphenyl) phosphite,
4,4'-Butylidene bis(3-methyl-o-tert-butylphenyl ditridecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phenyl phosphite, tridodecyl mercapto phosphite, decaphenyl heptadipropylene These include glycol octaphosphite, dibutylpentaerythritol diphosphite, didecylpentaerythritol diphosphite, dioctylpentaerythritol diphosphite, etc. Specific examples of organic phosphate esters include nonylphenoxypolyethoxyphosphoric acid, Decylhydroxypolyethoxyphosphoric acid, octyloxypolyethoxyphosphoric acid, lauryloxypolyethoxyphosphoric acid, stearyloxypolyethoxyphosphoric acid, oleyloxypolyethoxyphosphoric acid, tert-butylphenoxypolyethoxyphosphoric acid, octylphenoxyphosphoric acid These include polyethoxyphosphoric acid, dinonylphenoxypolyethoxyphosphoric acid, dodecylphenoxypolyethoxyphosphoric acid, etc. Specific examples of organic tin compounds include mono(or di)methyltin tris(or bis)(iso octylthioglycolate), mono(or di)octyltin tris(or bis)(isooctylthioglycolate), mono(or di)butyltintris(or bis)(isooctylthioglycolate),
Mono(or di)methyltintri(or di)laurate, mono(or di)butyltintri(or di)laurate
Laurate, mono(or di)octyltin tri(or di)laurate, mono(or di)methyltin tris(or bis)(isooctylmalate),
Mono(or di)butyltin tris(or bis)
(isooctyl maleate, mono(or di)octyltin tris(or bis)(isooctyl maleate), mono(or di)methyltin tris(or bis)(2-mercatoethyl oleate, mono(or di) Methyltin tri(or di)oleate, mono(or di)alkyl( _C1-12 )tin sulfide,
Mono (or bis) (butyl acrylate) tin tris (or bis) (isooctyl thioglycolate), mono (or bis) (methyl acrylate) tin tris (or bis) (isooctyl thioglycolate), mono (or di ) alkyl (C _1-12 ) tin oxide, mono (or di) methyl tin maleate polymer, mono ( or di) butyl tin maleate polymer, mono ( or di) octyl tin maleate polymer, mono ( or di) alkyl ( C _1~12 ) Tin
β-Mercaptopropionate, mono (or di)
Alkyl ( _C1-12 ) tin thioglycolate, mono(or di) _alkyl ( _C1-12 ) tin tri(or di)
Mercaptoethanol, mono(or di)alkyl( _C1-12 )tintri(or di)ricinolate, mono(or di)alkyl( _C1-12 )tintri(or di)
These include oleate, an organic tin compound shown in Japanese Patent Publication No. 51-44149, and the like. Specific examples of organic or inorganic antimony compounds include tris(isooctylthioglycolate) antimony, monobutylantimony bis(isooctylthioglycolate) dibutylantimony mono(isooctylthioglycolate), tris(2-
mercaptoethyl oleate) antimony, antimony trioxide, etc. Examples of organic titanium compounds include tetrastearyl titanate, tetrakis(2-ethylhexyl titanate), isopropylisostearyl titanate, diisopropoxybis(acetylacetone)titanate, tributoxymonostearyltitanate, dihydroxybis(lacteiacide)titanate, and isopropyltrititanate. Decylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate,
Tetraisopropylbis(dioctylphosphite) titanate, Tetraoctylbis(ditridecylphosphite) titanate, Tetra(2,2
-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tris(dioctylpyrophosphate)ethylene titanate, (mono- or di)butyl titanium (tri- or di) laurate, (mono- or di)butyl titanium (tris or bis) isooctylthioglycolate, tetrakis(isooctylthioglycolate) titanium, tetrakis(dodecylmercaptoate) titanium, titanium dioxide, and the like. Specific examples of metal soaps include lithium, sodium, potassium, magnesium, calcium,
Strontium, barium, zinc, gadmium,
Saturated and unsaturated fatty acid salts, aromatic carboxylates with linear or side chains of aluminum, tin, and lead;
Polyhydric carboxylic acid salts and organic acid salts of these acids with substituents, meaning one or more metal salts selected from acidic salts, neutral salts, and basic salts, and examples of such organic acids include 5. ~30 unsubstituted, substituted, saturated,
Unsaturated aliphatic or aromatic carboxylic acids such as caproic acid, heptanoic acid, 2-ethylhexoic acid,
undecanoic acid, lauric acid, neotridecanoic acid,
myristic acid, pentadecanoic acid, palmitic acid,
Heptadecanoic acid, stearic acid, hydroxystearic acid, dihydroxystearic acid, tonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, montanic acid, nonacosanoic acid, melisic acid,
hentriacotanoic acid, synthetic mixed odd-numbered acids with 21 to 31 carbon atoms derived from α-olefin, oleic acid, ricinoleic acid, acrylic acid, linolenic acid,
Aliphatic carboxylic acids such as linoleic acid, crotonic acid, acetoacetic acid, isostearic acid, isooctylic acid, neoacid, octylic acid, malonic acid, adipic acid,
Dibasic acids such as azelaic acid, sebacic acid, phthalic acid, thiodipropionic acid, dithiopropionic acid, and these dibasic acids and substituted or unsubstituted alkyl alkoxy alcohols with linear or side chains having 1 to 8 carbon atoms, Semi-esters of cycloalkyl-, arylakyl-, aryl-, alkylaryl alcohols having 5 to 18 carbon atoms, benzoic acid,
Methylbenzoic acid, butylbenzoic acid, benzoylbenzoic acid, phenyl acetic acid, salicylic acid, fumaric acid, naphthoic acid, naphthalic acid, abietic acid, dihydroabietic acid, phenylstearic acid, pyrrolidonecarboxylic acid, cinnamic acid, p-tert-butyl Examples include cyclic acids such as benzoic acid, rosin acid, naphthenic acid, and dehydroacetic acid, and organic acids such as nonylphenol, octylphenol, t-butylphenol, and acetoacetic ester. Specific examples of epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized lard oil, epoxidized beef tallow oil, epoxidized cottonseed oil, epoxidized safflower oil, epoxidized whale oil, epoxidized tall oil, and epoxidized sunflower oil. oil, epoxidized fish oil, diacetomonoglyceride of epoxidized soybean oil, epoxidized diacetomonoolein, benzoyl epoxystearate, butyl epoxystearate, cyclohexyl epoxystearate,
Dihydrononyl epoxy stearate, 2-ethylbutyl epoxy stearate, methoxyethyl epoxy stearate, isodecyl epoxy stearate, isooctyl epoxy stearate,
Tetrahydrofuryl epoxystearate, phenyl epoxystearate, acetoxyethyl epoxystearate, butyl, n-octyl, isooctyl and 2-ethylhexyl esters of epoxytol oil, epoxytriacetomonolisinoleic acid glyceride, epoxystearic acid.
Tertiary-butylphenyl, 9,10-epoxystearate of 3,4-epoxycyclohexylmethanol, epoxystearyl benzoate, 9,10,12,13-diepoxystearate of 3,4-epoxycyclohexylmethanol , 2-ethyl-1,3-hexadiol ester of 3,4-epoxycyclohexylcarboxylic acid, di-n- of epoxyhexahydrophthalic acid
Esters such as butyl, di-n-hexyl, di-2-ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl,
3,4-epoxycyclohexylmethyl-3,4
-Epoxycyclohexane carboxylate,
3,4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-
These include methylcyclohexylmethyl)adipate and a condensate of epichlorohydrin and bisphenol A. Specific examples of processing aids and impact reinforcement agents include chlorinated polyethylene, ethylene propylene copolymer,
Ethylene vinyl acetate copolymer, styrene butadiene copolymer, acrylonitrile styrene copolymer, acrylonitrile butadiene styrene copolymer, acrylic acid ester butadiene styrene copolymer, methacrylic acid ester butadiene styrene copolymer, polystyrene, acrylic resin, etc. It is. Specific examples of lubricants include polyethylene wax,
These include paraffin waxes derived from petroleum or coal, higher fatty acids, higher alcohols, natural or synthetic polymer ester waxes, ethyl bisstearamide, and metal salts having lubricity other than the metal soaps mentioned above. Specific examples of fillers include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, and silicon. These include sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, activated clay, talc, clay, red iron silicate, asbestos, and antimony trioxide. Specific examples of organic compounds or their salts include:
2-phenylindole, diphenylthiourea,
Cetyl and stearyl β-aminocrotonic acid ester, 1,3 and 1,4-butanediol bisβ
-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester, isocyanuric acid and its derivatives such as tris(2
Nitrogen-containing compounds such as -hydroxyethyl) cyanurate, pentaerythritol, mannitol,
Polyhydric alcohols such as sorbitol, carboxylic acids such as benzoic acid, methylbenzoic acid, linoleic acid, maleic acid, cinnamic acid, p-tert-butylbenzoic acid, crotonic acid, boric acid esters, thiodiglycolic acid esters, acetylacetone, cylindrical β-diketones such as benzoylmethane and benzoylacetone and their metal salts, acetoacetate, dehydroacetic acid or its esters or metal salts, pentaerythritol tetrakis (mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), dicyandiamide, tannins, Oxalic acid ester, malonic acid ester 2-
(3'-Methoxy-4'-hydroxyphenyl)indole, thiodipropionate esters such as dilaurylthiodipropionate, distearylthiodipropionate, 6-anilino-1,3,5-
triazine-2,4-dithiol, 6-butylamino-1,3,5-triazine-2,4-dithiol melamine, 2-mercaptoethyl oleate,
These include octylthioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, thioglycolic acid, and hexamethylenetetramine. Next, the stabilizing effect of the polyvinyl chloride resin according to the present invention will be shown by Examples. In the following examples, evaluation of plate-out is based on the following criteria. 0: No plate-out at all 1: Very slight plate-out 2: Slight plate-out 3: Obvious plate-out 4: Slightly significant plate-out 5: Significant plate-out Evaluation of initial coloration, mid-term coloration, and heat resistance is based on the following criteria. following. The initial coloration here refers to the degree of coloration after 5 minutes of the gear oven test, and the intermediate coloration refers to the degree of coloration after 15 minutes. 0: None Color 1: Slight yellow 6: Brown Color 2: Slight yellow 7: Brown 3: Yellow 8: Dark brown 4: Slight yellowish brown 9: Blackish brown 5: Yellowish brown 10: Black Color Heat resistance is the time it takes to turn black shows. The blooming phenomenon is evaluated according to the following criteria. (Evaluation after soaking the sample in water for 24 hours and air drying) 0: No blooming at all, 1: Very slight blooming 2: Slight blooming 3: Obvious blooming 4: Somewhat significant blooming 5: Significant blooming Weather resistance evaluation is based on weather resistance. The sample is irradiated with ultraviolet light using a meter, and observation shows the time until the sample begins to deteriorate. The four exemplified compounds of the present invention were prepared as follows: No. 1,
Shown as 2, 3, 4. 1,1,3-Tris [(2'-methyl-4'-di-
Tridecylphosphite-5-tertiarybutyl)phenyl]butane No. 1 Trisnonyl phenyl phosphite No. 2 4,4'-isopropylidene diphenolalkyl (C ₁₂ - C ₁₅ ) phosphite No. 3 Diphenyl phosphite Phite No. 4 Example 1 Add the exemplified compounds to the basic formulation below, dry blend, and knead for 5 minutes with a mixing roll at 175°C.
A 0.4mm sheet was created. 180 each sheet piece
A gear oven test was conducted under the condition of ℃. Basic blend PVC (=1050) 100 parts by weight Dioctyl phthalate 50 〃 Epoxidized soybean oil 2 〃 Calcium stearate 0.5 〃 Zinc stearate 0.5 〃 Subsequently, several of these roll sheets were stacked and heated at 175℃ - 100Kg using a compression molding machine /cm ² - Thickness under the condition of 10 minutes
A 2.0mm press sheet was created. At this time, heat resistance, initial coloring, mid-term coloring, blooming,
The weather resistance and plate-out results are shown in Table 1.

【table】

[Table] Example 2 Add the exemplified compounds to the following basic formulation, dry blend, and knead for 5 minutes with a mixing roll at 175°C.
A 0.4mm sheet was created. 180 each sheet piece
A gear oven test was conducted under the condition of ℃. Basic blend PVC (=1050) 100 parts by weight MBS 10 ABS 3 Dioctyltin bis(2-ethylhexylthioglycolate) 0.2 Calcium stearate 0.5 Zinc stearate 0.5 Next, several of these roll sheets were stacked and heated. Thickness molded using compression molding machine at 175℃ - 100Kg/cm ² -10 minutes
A 2.0mm press sheet was created. Table 2 shows the results of heat resistance, initial colorability, intermediate colorability, weather resistance, and plate-out.

【table】

【table】

Claims (1)

[Scope of Claims] 1 Polyvinyl chloride resin, 1,1,3-tris[(2'-methyl-4'-di-tridecylphosphite-5-tert-butyl)phenyl]butane and tris A polyvinyl chloride resin stabilizing composition characterized by containing nonylphenyl phosphite and/or 4,4'-isopropylidene diphenolalkyl (C ₁₂ -C ₁₅ ) phosphite. 2 Polyvinyl chloride resin, 1,1,3-tris[(2'-methyl-4'-di-tridecylphosphite-5-tert-butyl)phenyl]butane, trisnonyl phenyl phosphite and or 4,4'-isopropylidene diphenolalkyl (C ₁₂ -C ₁₅ ) phosphite, and further contains diphenyl phosphite.