JPH0335330B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for halogen-containing resins. More specifically, the present invention relates to a stabilizer for halogen-containing resins that has excellent coloring resistance, and has improved heat resistance, weather resistance, and a phenomenon unique to roll surfaces (plate-out phenomenon) and additive blow-out phenomenon (blooming phenomenon). It is well known that halogen-containing resins become colored due to heating during molding or photodeterioration, mainly caused by ultraviolet rays, after they are made into processed products, and cannot be used as 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 halogen-containing resins is wide-ranging in addition to the above-mentioned heat and light performance. Conventionally used stabilizers have various characteristics in terms of their effects, and no stabilizer that is fully satisfactory has 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 mercury 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 depending on the 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 and thermal processing becomes unstable. As a result of various studies, the present inventors found that the present invention is characterized by containing one or more complex compounds of a diketo acid ester compound represented by the following general formula and a metal element of ~ or of the periodic table. Stabilizer for halogen-containing resins. general formula

[Formula] (However, R ₁ , R ₂ , and R ₃ represent an alkyl group, an alkenyl group, an aryl group, an alkoxyalkyl group, and a substituent on these groups, even if they are the same or different. Good. Also, R ₃ is M may represent a metal element of ~ or group of the periodic table, and n is an integer including 0 and corresponds to the valence of the metal. ), as specifically shown in the examples, it was found that the coloring resistance and weather resistance were significantly improved, and the heat resistance, blooming, and plate-out phenomena were significantly improved, leading to the present invention. The present inventor previously discovered the stabilizing effect of diketo acid esters shown in JP-A No. 56-53144, but in the present invention, by forming a complex compound with a specific metal, it is further selective to halogen-containing resins. It shows a great effect. For example, even a small amount of Zn salt can improve the initial coloring.
Ca salt improves heat resistance. Such slightly different selective performance plays an important role when commercializing halogen-containing resins. In the present invention, each of the claimed complex compounds is added to 100 parts by weight of the halogen-containing resin.
It is preferable to use it in a proportion of 0.005 to 5 parts by weight. The compounds shown in the present invention are complex compounds, and various compounds are formed depending on the ligand represented by the general formula and the central metal surrounding it. Examples are shown in the table below. Here, R ₁ , R ₂ , and R ₃ in the table are shown in the general formula of the claims, and the metal elements in the table are central elements of the complex compound. Furthermore, M in R ₃ is also represented by the general formula in the claims. These compounds can be produced by reacting a diketo acid ester with a metal oxide or the like. Stabilizers for halogen-containing resins are sometimes used singly, but multiple stabilizers are mixed together (one-
In some cases, raw materials are reacted simultaneously to produce a packaged product. These manufacturing processes require multiple raw materials (e.g., diketo acid esters, β-diketones,
When obtaining the compound of the present invention using a fatty acid, an organic phosphite, an epoxy compound, and a metal oxide, for example, a compound having a structure that forms a salt of a diketo acid ester and a fatty acid with a metal sandwiched therebetween may be used as a substituent. However, in this case as well, it can be used as the composition of the present invention.

【table】

[Table] Halogen-containing resins to be stabilized in the present invention are polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinyl bromide, polyvinylidene bromide, brominated polyethylene, bromine Homopolymers such as fluorinated polypropylene, polyvinyl fluoride, polyvinylidene fluoride, chlorinated rubber, post-chlorinated polyvinyl chloride, or halogenated monomers that can be copolymerized such as vinyl chloride, vinyl acetate, ethylene, propylene, styrene, isobutylene, Isobrene, butadiene, methylstyrene, maleic acid, maleic ester, acrylic ester, methacrylic ester, acrylonitrile, vinyl urarate, lauryl vinyl ether, vinylidene chloride, chlorinated ethylene, chlorinated propylene, vinyl bromide, bromide These include multidimensional copolymers with two or more arbitrarily selected from vinylidene, vinyl fluoride, vinylidene fluoride, etc., and polymer blends of these with each other or with other polymers. The stabilizer of the present invention may contain one or more other commonly used stabilizers or additives. These include, for example, plasticizers, organic phosphites, organic phosphates, organic tin compounds, organic or inorganic antimony compounds, organic or inorganic titanium compounds, metallic soaps, epoxy compounds, ultraviolet absorbers, antioxidants, and viscosity adjusters. agent,
Pigments, dyes, processing aids, impact reinforcement agents, mold release agents,
Surface treatment agents, anti-bacterial agents, violet brighteners, antifogging agents, anti-drop agents, anti-drop agents, antistatic agents, polyhydric or higher alcohols, saturated and unsaturated fatty acids with linear or side chains, etc. organic solvents, lubricants, fillers, flame retardants, fragrances, organic compounds or their salts, crosslinking agents, plate-out inhibitors, etc. Among the above, specific examples of organic phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triisooctyl phosphite, tridecyl phosphite, and tri-2-ethylhexyl phosphite. , tridecyl phosphite, tri(octylphenyl) phosphite, tricyclohexyl phenyl phosphite, triscyclohexyl phosphite, tridecyl thiophosphite, triisodecyl thiophosphite, phenyl di-2
- Ethylhexylphosphite, phenyl diisodecylphosphite, phenyl dicyclohexylphosphite, phenyl diisooctylphosphite, phenyl di(tridecyl)phosphite, phenyl dicyclohexylphosphite, diphenyl isooctylphosphite,
diphenyl 2-ethylhexyl phosphite,
Diphenyl isodecyl phosphite, diphenyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl tridecyl thiophosphite, nonylphenyl di(tridecyl) phosphite, phenyl p-tert-butyl dodecyl phosphite, diisopropyl phosphite 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-tertiarybutylphenyl) phosphite, tetra(tridecyl)-4,
4'-Butylidene bis(2-tert-butyl-
5-methylphenyl) diphosphite, tetraisooctyl [4,4'-thiobis(2-tertiarybutyl-5-methylphenol)] diphosphite, tetranonylphenyl polypropylene glycol diphosphite, 1,1,3-tris [(2 '-Methyl-4-ditodecylphosphite-5
-tertiarybutyl)phenyl]butane, 4,
4'-Isopropylidene diphenolalkyl ( _C12 - _C15 ) phosphite, 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 (dipyropylene glycol) octaphosphite, decafenyl heptadipropylene glycol octaphosphite, tetrakis (isooctoxycarbomethylenethio) 1,2-oxycarbonylmethylene Thioethylene diphosphite, dibutoxycarboethylenethio (pentaerythritol tetrathioglycol) diphosphite, diisooctoxycarbomethylenethio (pentaerythritol tetrathioglycol) diphosphite, tetrakis (mercaptrauryl) 1,2-dimercapto-ethylene diphos 1,6-dimercapto-hexylene diphosphite, tetrakis (mercaptouralyl), tetrakis (mercaptouralyl)
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- tertiarybutyl-4-hydroxyphenyl) p-cumenylbis(p-nonylphenyl)phosphite, 4,4'-butylidenebis(3-methyl-O-
Tertiary-butylphenyl ditridecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phenyl phosphite, tridodecyl mercaptophosphite,
These include decaphenyl heptadipropylene glycol octaphosphite, dibutyl pentaerythritol diphosphite, didecyl pentaerythritol diphosphite, dioctyl pentaerythritol diphosphite. Specific examples of organic phosphate esters include nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid, octyloxypolyethoxyphosphoric acid, lauryloxypolyethoxyphosphoric acid, stearyloxypolyethoxyphosphoric acid, and oleyloxyphosphoric acid. These include polyethoxyphosphoric acid, tert-butylphenoxypolyethoxyphosphoric acid, octylphenoxypolyethoxyphosphoric acid, dinonylphenoxypolyethoxyphosphoric acid, and dodecylphenoxypolyethoxyphosphoric acid. Specific examples of organic tin compounds include mono(or di)methyltin tris(or bis)(isooctylthioglycolate), mono(or di)octyltintris(or bis)(isooctylthioglycolate), (or di)butyltin tris(or bis)(isooctylthioglycol), mono(or di)methyltintri(or di)laurate, mono(or di)butyltintri(or di)laurate, mono(or di)octyltintris (or di)laurate, mono(or di)methyltin tris(or bis)(isooctylmalate), mono(or di)butyltin tris(or bis)(isooctylmalate), mono(or di)octyltin Tris(or bis)(isooctylmalate), mono(or di)methyltin tris(or bis)(2
-mercaptoethyl 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)(isooctylthioglycolate), mono(or bis)( methyl acrylate) tin tris( _or bis)(isooctylthioglycol), mono(or di)alkyl( _C1-12 ) 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 ( _C1-12 ) tin-β-mercaptopropylene pionate, 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 )
₁₂ ) Tin tri(or di)ricinolate, mono(or di)alkyl ( _C1-12 ) tin tri(or di)oleate, organic tin compounds shown in JP-A-51-44149 _, and the like. Specific examples of organic or inorganic antimony compounds include tris(isooctylthioglycol)antimony, monobutylantimonybis(isooctylthioglycol)dibutylantimonymono(isooctylthioglycolate), and 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, cadmium,
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 having substituents, meaning one or more metal salts selected from acidic salts, neutral salts, and basic salts, and examples of the organic acids. 5 to 30 unsubstituted, substituted, saturated, or unsaturated aliphatic or aromatic carboxylic acids, including caproic acid, heptanoic acid, 2-ethylhexoic acid, undecanoic acid, lauric acid, neotridecanoic acid, myristic acid, and pentadecanoic acid. , palmitic acid, hepetadecanoic 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, hentriacotanic acid, synthetic mixed odd-numbered acids with 21 to 31 carbon atoms derived from α-olefin, oleic acid, ricinoleic acid , aliphatic carboxylic acids such as acrylic acid, linolenic acid, linoleic acid, crotonic acid, acetoacetic acid, isostearic acid, isooctylic acid, neoacid, octylic acid, malonic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, thio Dibasic acids such as dipropionic acid and dithiopropionic acid, and these dibasic acids with a carbon number of 1
Substituted or unsubstituted alkyl alkoxy alcohols with 8 straight or side chains, semi-esters of cycloalkyl, arylalkyl, aryl, alkylaryl alcohols with 5 to 18 carbon atoms, benzoic acid, methylbenzoic acid Acid, butylbenzoic acid, benzoylbenzoic acid, phenyl acetic acid, salicylic acid, fumaric acid, naphthoic acid, naphthalic acid, abietic acid, dihydroapietic acid, phenylstearic acid, pyrrolidonecarboxylic acid, cinnamic acid, p
- Cyclic acids such as tert-butylbenzoic acid, rosin acid, naphthenic acid and dehydroacetic acid, and organic acids such as nonylphenol, octylphenol, t-butylphenol and acetoacetate. 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 diacetomonoolefin, benzoyl epoxystearate, butyl epoxystearate, cyclohexyl epoxystearate, dihydrononyl epoxystearate, 2-ethylbutyl epoxystearate, epoxy Methoxyethyl stearate, isodecyl epoxy stearate, isooctyl epoxy stearate, tetrahydrofuryl epoxy stearate,
Phenyl epoxy stearate, acetoxyethyl epoxy stearate, butyl, n-octyl, isooctyl and 2-ethylhexyl esters of epoxy tol oil, epoxy triacetomonolisinoleate glyceride, tert-butylphenyl epoxy stearate, 3,4-epoxy 9,10-epoxystearate of cyclohexylmethanol, epoxystearyl benzoate, 9,10,12,13-diepoxystearate of 3,4-epoxycyclohexylmethanol, 2 of 3,4-epoxycyclohexylcarboxylic acid -ethyl-1,3-hexa-diol ester, di- of epoxyhexahydrophthalic acid
Esters such as n-butyl, di-n-hexyl, di-2-ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-
6-methylcyclohexylmethyl)adipate,
It is a condensate of epichlorohydrin and bisphenol A, etc. Specific examples of processing aids and impact strengthening agents include chlorinated polyethylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene butadiene copolymer, acrylonitrile styrene copolymer,
acrylonitrile butadiene styrene copolymer,
Examples include acrylic acid ester butadiene styrene copolymer, methacrylic acid ester butadiene styrene copolymer, polystyrene, and acrylic resin. 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, ethylene bisstearamide, and metal salts having lubricity other than the metal soaps mentioned above. Examples of fillers include oxides, hydroxides, chlorides, sulfides, carbonates, sulfates, sulfites, phosphates, phosphites, silicates of metals from groups ~ or groups of the periodic table. , nitrates, nitrites, and borates may also be used in combination. Specific examples include calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc chloride, zinc hydroxide, zinc carbonate, zinc sulfide, zinc phosphite, zinc borate, magnesium oxide, magnesium hydroxide, magnesium carbonate, Aluminum oxide, aluminum hydroxide, alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, activated clay, talc, clay, red iron, asbestos, antimony trioxide,
Barium hydroxide, barium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium sulfate, etc. 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 bis β
-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, β-diketones such as benzoylmethane and benzoylacetone and their metal salts, acetoacetate, diketoate ester, dehydroacetic acid or its ester or metal salt, pentaerythritol tetrakis (mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), Thiodipropionic acid esters such as dicyandiamide, tannins, oxalic acid esters, malonic acid esters, 2-(3'-methoxy-4'-hydroxyphenyl) indole, dilaurylthiodipropionate, distearylthiodipropionate, 6-anilino-1,3,5-triazine-2,4-dithiol, 6-butylamino-1,3,5-triazine-2,4-dithiol melamine, 2-mercaptoethyl oleate, octylthioglycolate,
These include 2-mercaptoethanol, β-mercaptopropionic acid, thioglycolic acid, hexamethylenetetramine, and the like. Next, the stabilizing effect of the halogen-containing 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: Colorless 6: Brown 1: Slight yellow 7: Brown 2: Slight yellow 8: Dark brown 3: Yellow 9: Dark brown 4: Slight yellowish brown 10: Black 5: Yellowish brown Heat resistance indicates the time it takes to turn black. 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 by weather meter It shows the time taken until the sample starts to deteriorate by irradiating it with ultraviolet rays and observing it. Example 1 Exemplary compounds were added to the basic formulation below, dry blended, and kneaded 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-ethylhexyl malate ester) 0.2 〃 Calcium stearate 0.5 〃 Zinc stearate 0.5 〃 Subsequently, several of these roll sheets were stacked and heated. Thickness molded using a 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 coloration, intermediate coloration, weather resistance, and plate-out.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A halogen-containing compound characterized by containing one or more complex compounds of a diketo acid ester compound represented by the following general formula and a metal element of ~ or group of the periodic table. Stabilizer for resin. General formula [Formula] (However, R ₁ , R ₂ , and R ₃ represent an alkyl group, an alkenyl group, an aryl group, an alkoxyalkyl group, and a substituent on these groups, and these groups may be the same or different. Also, R ₃ is M may represent a metal element of ~ or group of the periodic table, and n is an integer including 0 and corresponds to the valence of the metal. )