JPS6118577B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a light stabilizer for synthetic resins, and more particularly to a light stabilizer for synthetic resins comprising a combination of a sterically hindered cyclic amine compound and a co-active agent thereof. polyethylene, polypropylene, ABS resin,
It is known that synthetic resins such as polyvinyl chloride resins are sensitive to ultraviolet rays, and the effects thereof cause deterioration of color, decrease in mechanical strength, etc., and that they cannot withstand long-term use. In order to prevent these harmful effects, compounds such as benzophenone, benzotriazole, benzoate, and piperidine have been used so far, but many of these compounds color the resin, and The effect was also insufficient, and further improvements were desired. Among these compounds, piperidine-based compounds have attracted particular attention in recent years because they are non-coloring and act not as ultraviolet absorbers but as quenchers. However, although sterically hindered cyclic amine compounds such as piperidine compounds are relatively excellent light stabilizers, they are still insufficient for practical use. For example, it is known that piperidine-based compounds have relatively little effect when added in small amounts, and that a certain amount or more must be added. However, if the amount added is increased too much,
This is not preferable because it adversely affects the thermal stability, physical properties, etc. of the resin. It has also been proposed to use piperidine-based compounds in combination with benzophenol-based, benzotriazole-based, and other ultraviolet absorbers, but the effects were only additive. For that reason,
There has been a strong desire to develop a compatibilizing agent that increases the effectiveness of sterically hindered amine compounds. As a result of extensive studies in view of the current situation, the present inventors have found that (a) at least one sterically hindered cyclic amine compound represented by the following general formula ();
(b) a group in the molecule

【formula】

[Formula] and/or

The present invention was achieved by discovering that a combination of at least one type of monocyclic or fused heterocyclic compound containing [Formula] as part of the ring structure acts reciprocally and becomes an extremely excellent light stabilizer. . (In the formula, Y is a hydrogen atom, -O., an alkyl group,
Indicates a substituted alkyl group, alkenyl group, aralkyl group or acyl group. A is the base

【formula】

【formula】 or

[Formula] is shown, and R ₁ represents a lower alkyl group. Z is -O- or

[Formula] is shown, and R ₂ represents a hydrogen atom or a lower alkyl group. n represents 1 to 6. represents a residue derived from an organic carboxylic acid or an inorganic oxyacid. Also, when n=1

[Formula] is a group

[Formula] may be represented, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, or a substituted alkyl group. ) The above light stabilizer of the present invention will be explained in detail below. Many sterically hindered amine compounds represented by the above general formula () used in the present invention are known; for example, compounds described in the following patent publications can be used. I can do it. Special Publications Showa 44-26182, Showa 45-35661, Showa 46-
22105, 46-42618, 46-43304, 47-
8539, JP-A No. 47-6962, No. 48-7035, No. 48-
65180, 48-65182, 48-72240, 48-
95986, 49-8539, 49-21389, 49-
61235, 49-61236, 49-61237, 49-
61238, 49-64635, 49-72332, 50-
116529, 50-138041, 51-88484, 51-
126385, 51-132242, 52-22578, 52-
63183, 52-71476 52-71477, 52-71486,
52-73886, 52-78876, 52-83377, 52
-89677, 52-112648. In the compound represented by the general formula () used in the present invention, examples of the alkyl group include methyl, ethyl, propyl, butyl, hexyl, octyl, etc., and examples of the substituted alkyl group include chloroethyl, hydroxyethyl, epoxypropyl, Examples of the aralkyl group include benzyl and phenylethyl; examples of the alkenyl group include vinyl and allyl; and examples of the acyl group include formyl and acetyl. Examples of lower alkyl groups include methyl, ethyl, propyl, and butyl. Examples of the organic carboxylic acid residue represented by are the following carboxylic acid residues. Acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, behenic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, linolenic acid, ricinolenic acid, hydroxyacetic acid, amino acid Acetic acid, aminocrotonic acid, phenyl acid, phenoxyacetic acid, 3,5-di-5-butyl-4-hydroxyphenylpropionic acid, laurylthiopropionic acid, benzoic acid, toluic acid, p-tert-butylbenzoic acid, p -Hydroxybenzoic acid, salicylic acid, p
-Chlorbenzoic acid, p-methoxybenzoic acid, p-
Nitrobenzoic acid, 3,5-di-tert-butyl-4-
Hydroxybenzoic acid, nicotinic acid, isonicotinic acid, thiophene-2-carboxylic acid, pyrrolidonecarboxylic acid, piperidine 4-carboxylic acid, orotic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, speric acid, sebatine Acid, decamethylene dicarboxylic acid, maleic acid, itaconic acid, acetylene dicarboxylic acid, bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid, thiodipropionic acid, thiodiglycolic acid,
methylenebisthioglycolic acid, iminodiacetic acid,
Tartaric acid, malic acid, thiomalic acid, dihydrotartaric acid, epoxysuccinic acid, 3,4-dioxythiophenedicarboxylic acid, 1,4-biscarboxyethylpiperazine, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro Phthalic acid, 5-bicyclo[2.2.1.]heptene-2,
3-dicarboxylic acid, 5-bicyclo[2.2.2.]heptene-2,3-dicarboxylic acid, propanetricarboxylic acid, butanetricarboxylic acid, butenetricarboxylic acid, nitrilotriacetic acid, citric acid, triscarboxyethyl isocyanurate, triscarboxymethyl Isocyanurate, trimellitic acid,
Butanetetracarboxylic acid, ethylenetetracarboxylic acid, ethylenediaminetetraacetic acid, pyromellitic acid, 1,3-bis(aminomethyl)cyclohexane-N,N,N',N'-tetraacetic acid. Examples of the inorganic oxyacid residue represented by include the following inorganic oxyacid residues. Examples include phosphoric acid, phosphorous acid, phosphonic acid, phosphonic acid, substituted phosphonic acid, substituted phosphonic acid, silicic acid, diorganosilicic acid, boric acid, and carbonic acid. Further, some of the acid groups of the organic carboxylic acids and inorganic oxygen acids may be esters of monovalent or polyvalent phenols or alcohols. When the ester is an ester of a polyhydric phenol or a polyhydric alcohol, two or more organic carboxylic acids or inorganic oxygen acids are combined with the polyhydric phenol or polyhydric alcohol as shown in the following formula. They may be connected together.

【formula】

(1 is an integer of ~10, m is an integer of 0 to 2, and indicates a residue in a polyhydric phenol or polyhydric alcohol.) Examples of the residues of the polyhydric phenol or polyhydric alcohol represented above include the following: Examples include residues of polyhydric phenols or polyhydric alcohols. Examples of polyhydric phenols include hydroquinone, 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-cyclohexylidene diphenol, 4,4'-methylenebisphenol, 4,4'-sulfobis Phenol, 2,5-di-tertiary butylhydroquinone, 2,3,6-trimethylhydroquinone, 2-methylresorcin,
2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-
ethyl-6-tert-butylphenol), 2,2'-
Methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-n-butylidenebis(4,6-di-methylphenol),
Bis-1,1-(2'-hydroxy-3',5'-di-
methylphenyl)-3,5,5-trimethylhexane, 2,2'-cyclohexylidenebis(4-ethyl-6-tert-butylphenol), 2,2'-isopropylbenzylidene-bis(4-ethyl-6
-tert-butylphenol), 2,2'-thiobis(4-tert-butyl-6-methylphenol), 2,
2'-thiobis(4-methyl-6-tert-butylphenol), 2,2'-thiobis(4,6-tert-butylphenol), 4,4'-methylenebis(2-methyl-6-tert-butylphenol) phenol), 4,4'-isopropylidene (2-phenylphenol),
4,4′-n-ptylidene bis(3-methyl-6-
tertiary butylphenol), 4,4'-cyclohexylidene bis(2-tertiary butylphenol), 4,
4'-cyclohexylidene bis (2-cyclohexylphenol), 4,4'-benzylidene bis (2
-tert-butyl-5-methylphenol), 4,
4'-oxobis(3-methyl-6-isopropylphenol), 4,4'-thiobis(2-methyl-
6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,
4'-sulfobis(3-methyl-6-tert-butylphenol), bis(2-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 1,
1,3-tris(2'-methyl-4'-hydroxy-
5'-tert-butylphenyl)butane, 2,2-bis(3'-tert-butyl-4'-hydroxyphenyl)-
4-(3″,5″,-di-tert-butyl-4″-hydroxyphenyl)butane, 2,2-bis-(2′-methyl-5′-tert-butyl-4′-hydroxyphenyl) )
Examples include -4-(3″,5″-di-tert-butyl-4′-hydroxyphenyl)butane. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-
Propanediol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol, thiodiethylene glycol, 1,6-hexanediol, 1,10-
Decanediol, 1,4-cyclohexanediol, 1,4-diclohexanedimethanol, 1,
Examples include 4-phenyldimethanol, hydrogenated bisphenol A, glycerin, trimethylolmethane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, and the like. In addition, monovalent phenols include phenol, cresol, 4-tert-butylphenol, octylphenol, nonylphenol, 2,4-
Examples include di-tert-butylphenol and 2-cyclohexylphenol. Monohydric alcohols include methanol, ethanol, octanol, 2-ethylhexanol, cyclohexanol, decanol, lauryl alcohol, tetradecanol, hexadecanol, octadecanol, methoxyethanol, ethoxyethanol, butoxyethanol, and phenolic alcohol. diethanol, ethoxyethoxyethanol,
Examples include butoxyethoxyethanol. Examples of the compound represented by the formula () used in the present invention include those shown below. -1 4-benzoyloxy-2,2,6,6
-tetramethylpiperidine, -2 4-salicyloyloxy-2,2,6.6-
Tetramethylpiperidine, -3 4-caproyloxy-2,2,6,6
-tetramethylpiperidine, -4 4-stearoyloxy-2,2,6,
6-tetramethylpiperidine, -5 4-(β-3',5'-di-tert-butyl-4'-
Oxyphenyl-propionyloxy)-2,
2,6,6-tetramethylpiperidine, -6 4-(3'-5'-di-tert-butyl-4'-oxybenzoyloxy)-2,2,6,6-tetramethylpiperidine, -7 4 -benzoyloxy-1,2,2,
6,6-pentamethylpiperidine, -8 4-salicyloyloxy-1,2,2,
6,6-pentamethylpiperidine, -9 4-stearoyloxy-1,2,2,
6,6-pentamethylpiperidine, -10 4-tert-butylbenzoyloxy-1,
2,2,6,6-pentamethylpiperidine, -11 bis-(2,2,6,6-tetramethyl-4-piperidyl)-separt, -12 bis-(2,2,6,6-tetramethyl -4-piperidyl)-sperate, -13 bis-(2,2,6,6-tetramethyl-4-piperidyl)-dodecanedioate, -14 bis-(1,2,2,6,6-tetramethyl -4-piperidyl)-sepacate, -15 4-capryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, -16 4-capryloyloxy-1-allyl-
2,2,6,6-tetramethylpiperidine, -17 4-benzoylamide-2,2,6,6
-tetramethylpiperidine, -18 4-acryloylamide-2,2,6,
6-tetramethylpiperidine, -19 4-stearoylamide-2,2,6,
6-tetramethylpiperidine, -20 N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalamide, -21 3-n-butyl-7,7,9,9-tetra Methyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, -22 3-n-butyl-8-methyl-7,7,
9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, -23 3-n-octyl-7,7,9,9-tetramethyl-1,3,8- triazaspiro [4.5] decane-2,4-dione, -24 3-n-octyl-8-methyl-7,
7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, -25 3-allyl-7,7,9,9-tetramethyl-1,3,8- triazaspiro[4.5]decane-2,4-dione, -26 tetra(2,2,6,6-tetramethyl-4-piperidyl)-1,3-bis(aminomethyl)cyclohexanetetraacetate, -27 3-glycidyl -7,7,9,9-tetramethyl-1,3,8-triazasubiro[4.5]decane-2,4-dione, -28 3-glycidyl-8-methyl-7,7,
9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, -29 3-octadecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[ 4.5] Decane-2,4-dione, -30 3-cyclohexyl-7,7,9,9-
Tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, -31 1,3,8-trimethyl-7,7,9,
9-Tetramethyl-1,3,8-triazaspiro [4.5] Decane-2,4-dione, -32 8-Methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] Decane-2,4-dione, -33 3-n-octyl-8-benzyl-7,
7,9,9-tetramethyl-1,3,8-trisazaspiro[4.5]decane-2,4-dione, -34 2,4,6-tris-(2,2,6,6
-tetramethyl-4-piperidyloxy)-s
-triazine, -35 2,4,6-tris-(1,2,2,
6,6-pentamethyl-4-piperidyloxy)-s-triazine, -36 2,4,6-tris-(2,2,6,6
-tetramethyl-4-piperidylamino)-s
-triazine, -43 1,2,2,6,6-pentamethyl-4
-Lauroyloxy-piperidine, -38 Bis-(2,2,6,6-tetramethylpiperidinyl-4)aziboyl-dihydrazone, -39 2,2,6,6-tetramethylpiperidinyl-4-capryloyl -Hydrazone, -40 2,2,6,6-tetramethyl-4-benzoylpiperidine-1-oxyl, -41 Bis(2,2,6,6-tetramethyl-
4-Piperidinyl-1-oxyl)-sebacate, -42 Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, -43 Tris(2,2,6,6-tetramethyl-4- piperidyl)butanetricarboxylate, -44 Tetra(2,2,6,6-tetramethyl-4-piperidyl)butanetetracarboxylate, -45 Tris(2,2,6,6-tetramethyl-4-piperidyl) trimellitate, -46 Tetra(2,2,6,6-tetramethyl-4-piperidyl) Viromellitate, -47 Bis(2,2,6,6-tetramethyl-
4-piperidyl) terephthalate, -48 bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)methyliminodiacetate, - 49 Tris(2,2,6,6-tetramethyl-4-piperidyl) citrate, -50 Tris(2,2,6,6-tetramethyl-4-piperidyl) phosphite, -51 Bis(2,4-diperidyl) -tert-butylphenyl)-2,2,6,6-tetramethyl-4-piperidylphosphite, -52 bis(2,2,6,6-tetramethyl-
4-piperidyl) pentaerythritol diphosphite, -53 bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl ), pentaerythritol diphosphite, -54 tetra(2,2,6,6-tetramethyl-4-piperidyl), bisphenol A diphosphite, -55 tetra(9-aza-8,8,10,10-tetra Methyl-3-methyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)・4,
4'-Ptylidenebis(2-tert-butyl-5-methylphenol) diphosphite, -56 tetra(2,2,6,6-tetramethyl-4-piperidyl)/1,6-hexanediol diphosphite, - 57 Hexa(9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5]
-3-undecylmethyl)・1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, -58 hexa(2,2,6,6-tetramethyl- 4-piperidyl)/tris(2-hydroxyethyl)isocyanurate/triphosphite, -59 Tetra(2,2,6,6-tetramethyl-4-piperidyl)/Neopentyl glycol diphosphite, -60 Tetra(2, 2,6,6-tetramethyl-4-piperidyl)・Hydrogenated bisphenol A・
Diphosphite, -61 Tetra(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl), hydrogenated bisphenol A, diphosphite, - 62 Tris(2,2,6,6-tetramethyl-4-piperidyl)phosphate, -63 Bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5 ]-3-undecylmethyl) pentaerythritol diphosphate, -64 3,5-di-tert-butyl-4-hydroxypenzyl-bis(2,2,6,6-tetramethyl-4-piperidyl)phosphonate , -65 phenyl-bis(2,2,6,6-tetramethyl-4-piperidyl)phosphinate, -66 tris(2,2,6,6-tetramethyl-4-piperidyl)borate, -67 bis(2 ,2,6,6-tetramethyl-
4-piperidyl)dimethylsilicate, -68 bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)carbonate, -69 bis (2,2,6,6-tetramethyl-
4-piperidyl) carbonate, -70 bis(2,2,6,6-tetramethyl-
4-piperidyl)・4,4′-butylidenebis(2-tert-butyl-5-methylphenol)・dicarbonate, 71 bis(9-aza-8,8,10,10-tetramethyl-3-ethyl- 1,5-dioxaspiro[5.5]-3-undecylmethyl), hydrogenated bisphenol A, dicarbonate, -72 bis(9-aza-8,8,10,10-tetramethyl-3-methyl-1, 5-Dioxaspiro[5.5]-3-undecylmethyl) ethylene glycol dicarbonate, which is a component used as a compensating agent for the above compound () in the present invention, contains groups in the molecule.

【formula】

[Formula] and/or teeth

A monocyclic or fused ring compound containing [Formula] as part of the ring structure will be explained in more detail. Examples of the basic skeletons of these compounds include those shown below.

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[Formula] These compounds may have various substituents on the basic skeleton. Examples of these substituents include alkyl groups, aryl groups, aralkyl groups, aralyl groups, alkenyl groups, hydroxyl groups, halogen atoms, amino groups, nitro groups, carbonyl groups, and acylamino groups. Specific examples of these compounds (compounding agents) include those shown below.

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[Formula] The light stabilizer of the present invention is added in an amount of 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the synthetic resin to be stabilized. The ratio of added sterically hindered cyclic amine to compatibilizer is 1:100 to 100:1, preferably 1:10 to 20:1. Examples of the synthetic resins stabilized by the present invention include α-
Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer, and their copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorine polypropylene, polyvinylidene fluoride, 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-isobrene copolymer, vinyl chloride-chlorinated propylene copolymer, Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-
Acrylic acid ester copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, polystyrene, Polyvinyl acetate, acrylic resin, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers , methacrylic acid ester-butadiene-styrene copolymer, methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, or phenol resin, Examples include urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-
Rubbers such as butadiene copolymer rubber and styrene-butadiene copolymer rubber, or blends of these resins may also be used. Also included are crosslinked synthetic resins such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed synthetic resins such as foamed polystyrene foamed with a foaming agent. Oxidative stability can be further improved by further using a phenolic antioxidant in combination with the light stabilizer of the present invention. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-
Cresol, stearyl-(3,5-di-methyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5
-di-tert-butylphenyl) propionate, distearyl (4-hydroxy-3-methyl-5-
(tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol),
butylphenol), 2,2′-methylenebis[6
-(1-methylcyclohexyl)p-cresol], bis[3,3-bis(4-hydroxy-3
-Tertiary butylphenyl) petitlic acid] glycol ester, 4,4'-butylidene bis(6-
tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(3,5-di-tert-butyl) -4-hydroxybenzyl)-2,4,6-trimethylbenzene, 3,
9-bis-[1,1-dimethyl-2-(3,5-
Di-tert-butyl-4-hydroxyphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, tetrakis[methylene-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3 ,5-Tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-
Examples include hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine and 4,4'-thiobis(6-tert-butyl-m-cresol). A sulfur-based antioxidant can also be used in combination with the stabilizer of the present invention. Examples of the sulfur-based antioxidant include distearylthiodipropionate, dilaurylthiodipropionate, pentaerythritol tetralaurylthiopropionate, and the like. A phosphite compound can also be used in combination with the stabilizer of the present invention. Examples of the phosphite-based compounds include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, trioctyl phosphite, and trilauryl phosphite. , tridecyl phosphite, octyl-diphenyl phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-
1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra( _C12-15 mixed alkyl)-4,
4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidene bis(3-methyl-6-tert-butylphenol)
Diphosphite, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, tris(mono-di mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis( octylphenyl)・bis[4,4′-butylidenebis(3-methyl-6-tert-butylphenol)]・1,6-hexanediol diphosphite, phenyl・4,
Examples include 4'-isopropylidene bis(2-tert-butylphenol) di(nonylphenyl) phosphite. The effect can be enhanced by further using the stabilizer of the present invention with an ultraviolet absorber. Examples of these ultraviolet absorbers include 2
-Hydroxy-4-methoxybenzophenyne, 2
-Hydroxybenzophenones such as hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-(2' ―
Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-
(2'-Hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-
(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-
Benzotriazoles such as di-t-amyl phenyl) benzotriazole, phenyl salicylate, pt-butylphenyl salicylate, 2,
4-di-t-butylphenyl-3,5, di-t-
Butyl-4-hydroxypenzoates, 2,
2'-thiobis(4-t-octylphenol)Ni
salt, [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine Ni salt, (3,5
-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt and other nickel compounds and substituted acrylonitriles. If necessary, the stabilizer of the present invention may include a polymerization group deactivator, a nucleating agent, a metal soap, an organic tin compound, a plasticizer, an epoxy compound, a pigment, a filler, a blowing agent, an antistatic agent, a lubricant. , processing aids, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are given for the purpose of illustration only and should not be construed as limiting the scope of the present invention. Example 1 After mixing the following formulation in a mixer for 5 minutes:
A compound was created using an extruder (cylinder temperature 230℃ and 240℃, head die temperature 250℃).
°C, rotation speed 20r.pm). Using this compound, test pieces of 95 x 40 x 1 mm were made using an injection molding machine (cylinder temperature: 240
℃, nozzle temperature 250℃, injection pressure 475Kg/cm ² ). Using the obtained sample, photostability was measured using a weatherometer. The results are shown in Table-1. Compound polypropylene resin (profax 6501 manufactured by Hercules) 100 parts by weight dilauryl thiodipropionate 0.3 Tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] methane 0.1 Formula ( ) Compound 0.2 Phase Surplus Agent 0.1

[Table] Example 2 The effect can be further enhanced by using the stabilizer of the present invention in combination with a conventional ultraviolet absorber. In this example, the same test as in Example 1 was conducted using the following formulation. The results are shown in Table-2. Blended polypropylene 100 parts by weight 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol) 0.2bis(2,2,6,6,-tetramethyl-4-
(piperidinyl) sebacate 0.1 3-salicyloylamino-1,2,4-triazole 0.1 Sample 0.1

[Table] Example 3 Compound Polypropylene 100 parts by weight Stearyl [3-(3,5-di-tert-butyl-
4-Hydroxyphenyl)propionate]
0.2 Compound of Formula () 0.3 Phase Surplus Agent 0.3 The above mixture was kneaded on a roll and then pressed to form a sheet with a thickness of 0.5 mm. The light resistance of this sheet was measured using a weatherometer. The results are shown in Table-3.

[Table] Example 4 Compound polyethylene 100 parts by weight Ca-stearate 0.1 distearylthiodipropionate 0.2 Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate 0.1 parts by weight of formula () Compound 0.15 Phase Surplus Agent 0.2 The above mixture was kneaded and pressed to form a sheet with a thickness of 0.5 mm. Using this sheet, the light resistance was measured in a weatherometer, and the time until it became brittle was measured. The results are shown in Table-6.

[Table] Example 5 Compound Ethylene-vinyl acetate copolymer resin 100 parts by weight Montanic acid lubricant 0.3 2,6-di-tert-butyl-p-cresol
0.1 Compound of Formula () 0.25 Phase Surplus Agent 0.05 The above mixture was kneaded with rolls and then pressed at 120°C to form a sheet with a thickness of 1.0 mm. This sheet was irradiated for 500 hours in a weatherometer, and the residual tensile strength was measured. The results are shown in Table-5.

【table】

[Table] Example 6 Compound Polyvinyl chloride 100 parts by weight Di-2-ethylhexyl phthalate 50 Ca-stearate 1.0 Zn-stearate 0.2 Compound of formula () 0.5 Phase surplus agent 0.2 The above mixture was kneaded on a roll. A sheet with a thickness of 1 mm was created. The sheet was tested for light resistance in a weatherometer. The results are shown in Table-6.

【table】

[Table] Example 7 Compound ABS resin 100 parts by weight Ca-stearate 0.5 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane
0.1 Compound of formula () 0.4 Phase surplus agent 0.2 Roll knead the above mixture and press it to a thickness of 3 mm.
I made a sheet. The residual tensile strength after 800 hours of irradiation was measured using a weatherometer using this sheet. The results are shown in Table-7.

[Table] Example 8 Compound Nylon 6 100 parts by weight Compound of formula () 0.2 Phase Surplus agent 0.02 After thoroughly mixing the above composition, it was pressed at 250°C to produce a 0.5 mm sheet. Using this sheet, the coloring of the sheet after 120 hours of irradiation in a weatherometer was checked to determine its light resistance. Display the results.
8.

[Table] Example 9 Compound Polybutylene terephthalate 100 parts by weight Trisnonyl phenyl phosphite 0.1 Compound of formula () 0.3 Phase remainder 0.2 The above blend was subjected to in-die excision processing at 250°C to prepare test pieces. Using this test piece, the residual tensile strength after 500 hours of irradiation was measured in a weatherometer. The results are shown in Table 9.

【table】

[Table] Example 10 Compound polyurethane resin (Asahi Denka U-100)
100 parts by weight 2,6-di-tert-butyl-p-cresol
0.1 Octyl diphenyl phosphite 0.2 Compound of formula () 0.3 Phase surplus agent 0.03 The above mixture was kneaded on a roll at 70°C for 5 minutes,
A sheet with a thickness of 5 mm was produced by pressing at 120°C for 5 minutes. The residual elongation of this sheet after 50 hours of irradiation was measured using a fade meter. Display the results.
Shown in 10.

【table】

Claims (1)

[Scope of Claims] 1 (a) at least one sterically hindered cyclic amine compound represented by the following general formula (); and (b)
A light stabilizer for synthetic resins comprising a combination of at least one type of monocyclic or condensed heterocyclic compound containing the groups [Formula] [Formula] and/or [Formula] as part of the ring structure in the molecule. (In the formula, Y is a hydrogen atom, -O., an alkyl group,
Indicates a substituted alkyl group, alkenyl group, aralkyl group or acyl group. A represents a group [Formula] [Formula] or [Formula], and R ₁ represents a lower alkyl group. Z represents -O- or [Formula], and R ₂ represents a hydrogen atom or a lower alkyl group. n represents 1 to 6. represents a residue derived from an organic carboxylic acid or an inorganic oxyacid. Further, when n=1, [Formula] may represent a group [Formula], and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, or a substituted alkyl group. )