JPS6214181B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized synthetic resin composition,
Specifically, α・having a polyalkylpiperidyl group
The present invention relates to a synthetic resin composition containing a β-unsaturated carboxylic acid ester (co)polymer and having improved photostability. polyethylene, polypropylene, ABS resin,
It is known that polymers such as polyvinyl chloride are generally sensitive to the effects of light, and are degraded by the effects of light, causing discoloration or a decrease in strength, and cannot withstand long-term use. In order to prevent the deterioration of polymers caused by this light, various stabilizers have been used in the past, but the stabilizing effect of the conventionally used light stabilizers is insufficient, and the stabilizers themselves are Many of them are unstable to heat or oxidation, are easily extracted from the polymer by solvents such as water, and many of them color the polymer. could not be stabilized over a long period of time. Among these conventionally used light stabilizers, hindered piperidine compounds are themselves non-coloring and have the characteristics of acting not as ultraviolet absorbers but as quenchers. Attention has been paid. For example, ester derivatives of hindered piperidin-4-ol were proposed in Japanese Patent Publication No. 46-42618;
Ketal derivatives of hindered piperidin-4-one are proposed in JP-A No. 82146 and Japanese Patent Publication No. 16980-1980, and esterified derivatives of N-hydroxyalkyl hindered piperidyl compounds are proposed in JP-A-50-35239. Disclosed. However, conventionally known piperidine-based compounds have insufficient photostabilizing ability, are highly volatile, are easily extracted from polymers by water, or do not interact with polymers. It also had drawbacks such as poor compatibility and causing blooming. In order to overcome these drawbacks, it has recently been proposed to use high molecular weight hindered piperidine compounds. For example, JP-A-52-141883 proposes polymers such as polyesters having hindered piperidyl groups, and JP-A-54-21489 and JP-A-54
JP-71185 proposes a (meth)acrylate polymer having a hindered piperidyl group. Further, JP-A-55-157612 proposes a polymer of a maleic acid derivative having a hindered piperidyl group. However, when these polymers are used, although the volatility of the stabilizer is reduced, the stabilizing effect is not sufficient, and the compatibility with the polymeric substance to be stabilized is poor, resulting in problems such as bloom. There were some drawbacks, and further improvements were needed. In view of the current situation, the present inventors have made extensive studies and found that α-・
The inventors have discovered that all of the above-mentioned drawbacks can be overcome by using a β-unsaturated carboxylic acid ester (co)polymer, and have arrived at the present invention. That is, in the present invention, for 100 parts by weight of synthetic resin,
A homopolymer of a substituted piperidine compound represented by the following formula () or (), or a homopolymer thereof;
The present invention provides a stabilized synthetic resin composition containing 0.001 to 5 parts by weight of a copolymer with a compound containing at least one polymerizable double bond. (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, R ₅ represents a hydrogen atom or an acyl group, and R ₆ represents a hydrogen atom, an oxyl group, an alkyl group, and a substituted alkyl group. group, R ₇ represents a hydrogen atom or a methyl group, X represents an alkylene group, Y represents an alkantriyl group, and n is 0
Or indicates 1. ) Hereinafter, the compounds used in the present invention will be explained in detail. The alkyl group represented by R ₁ to _{R 4} includes methyl, ethyl, propyl, isopropyl, butyl,
Examples include hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, and the like. Examples of the acyl group represented by _R5 include acetic acid, propionic acid, caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic 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, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids , mixtures of the above naturally occurring acids such as 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, p-t-butylbenzoic acid, 5-t- Examples include residues such as octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, monobutyl maleate, monodecyl phthalate, and cyclohexanecarboxylic acid. As the alkyl group represented by R ₆ , R ₁ to _{R 4}
Examples include groups similar to those listed in . Further, examples of the substituted alkyl group include groups such as hydroxyethyl, acetoxyethyl, 2,3-epoxypropyl, and benzyl. The alkylene group represented by X includes ethylene, 1,2-propylene, 1,3-propylene,
2,2-dimethylpropylene, 1,2-butylene, 1,2-hexylene, 1,2-octylene,
1,2-decylene, 1,2-dodecylene, 1,2
-tetradecylene, 1,2-hexadecylene,
Examples include 1,2-octadecylene, 2-methyl-2-hydroxymethyl-1,3-propylene, and 2-ethyl-2-hydroxymethyl-1,3-propylene. The alkantriyl group represented by Y is
Examples include residues of trihydric alcohols such as glycerin, trimethylolpropane, and trimethylolethane. Next, representative examples of compounds represented by the general formula () or () are shown in Table 1 below. Examples of the compound containing at least one polymerizable double bond constituting the copolymer component used in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylate. Acrylic acid methyl ester, methacrylic acid butyl ester, methacrylic acid decyl ester, methacrylic acid hydroxypropyl ester, acrylic acid glycidyl ester, ethylene glycol dimethacrylate, acrylic acid amide, acrylic acid methyl amide, acrylic acid octadecyl amide, dibutyl acrylate Amide, methacrylic acid amide, methacrylic acid octadecylamide, methacrylic acid diethylamide, methylenebisacrylamide, acrylonitrile, methacrylonitrile, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1- Decene, isoprene, butadiene, styrene, divinylbenzene, 2-vinylpyridine,
4-vinylpyridine, vinyl butyl ether, divinyl ether, N-vinyl-pyrrolidone-2,
Examples include N-vinylcarbazole, maleimide, bis-2,2,6,6-tetramethylpiperidyl maleate, 2,2,6,6-tetramethylpiperidyl acrylate, and unsaturated phosphonates. () formula or () used in the present invention
A homopolymer or copolymer of a compound represented by the formula refers to a homopolymer or copolymer having a repeating unit derived from the compound represented by the formula () or () in the polymer skeleton, and one or more of the above compounds. If necessary, polymerization is carried out using a conventional polymerization initiator such as an organic peroxide or an azonitrile compound together with a compound containing at least one other polymerizable double bond, or a polymer having an alkoxycarbonyl group and a polyalkyl Although it can be easily produced by a transesterification reaction with an alcohol having a piperidyl group, the present invention is not limited by the production method. The molecular weight of the homopolymer or copolymer according to the present invention is preferably 500 to 50,000, more preferably
It is 1000-20000. Next, a specific synthesis example of the polymer used in the present invention will be shown. Synthesis example 1 9-acryloyloxyethyl-9-aza-
Dissolve 3.4 g (0.001 mol) of 3,3-dimethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5,5]-undecane in 15 ml of toluene, and dissolve 0.04 g of azobisisobutyro Nitrile was added, and the mixture was heated and stirred at 90°C for 12 hours under a nitrogen stream. After confirming that the monomer has completely disappeared by gas chromatography analysis, remove the solvent under reduced pressure.
3.3 g of a light brown glassy solid (stabilizer No. 1) was obtained. As a result of analysis, the product had an N content of 4.10% (calculated value
4.13%), molecular weight 5300 (vapor pressure method), and softening point 90°C. Polymers shown in Table 2 below were synthesized by the same operations as in Synthesis Example 1. However, in order to control the molecular weight, the solvent and initiator were changed as appropriate, and a molecular weight regulator was used as necessary.

【table】

[Table] Synthesis example 2 Methyl acrylate oligomer (average molecular weight approx.
1100), 4.3 g, 9-hydroxyethyl-9-aza-3,3-dimethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5,5]-undecane 14.3 g and lithium amide 0.1 g was dissolved in 30 ml of pseudocumene, and the mixture was heated and stirred at 180°C for 40 hours. After cooling, wash with water, dry, remove solvent, and then
It was dried at 160°C and 1 mmHg for 3 hours to obtain a light brown resinous solid (stabilizer No. 23) with a softening point of 91°C. As a result of analyzing the product, the molecular weight was 4300, and the N content was
It was found that about 99% of the methyl ester was transesterified. Synthesis Example 3 In the same manner as in Synthesis Example 2, 6.4 g of n-butyl acrylate oligomer (average molecular weight approximately 2000) and 9-aza-3,8,8,10,10-pentamethyl-3-hydroxymethyl-1,5-dioxaspiro were prepared. [5・
5]-A pale yellow resinous solid was obtained from 12.9 g of undecane. This was dissolved in chloroform, and unreacted 9-aza-3,8,8,10,10-pentamethyl-3-hydroxymethyl-1,5-dioxaspiro[5,
5]-Undecane was removed to obtain a purified polymer (stabilizer No. 24). As a result of analyzing the product, the molecular weight was 4400 and the N content was
It was found that about 84% of the n-butyl ester had been transesterified, with a softening point of 78°C. Synthesis Example 4 In the same manner as in Synthesis Example 3, 6.4 g of n-butyl acrylate oligomer (average molecular weight approximately 2000) and 8.
8,9,10,10-pentamethyl-3-ethyl-3
A pale yellow resinous solid was obtained from 8.6 g of -hydroxymethyl-1,5-dioxaspiro[5,5]-undecane, and this was further purified into a polymer (stabilizer
No. 25) was obtained. As a result of analyzing the product, the molecular weight was 3600, and the N content was
It was found that about 52% of the n-butyl ester was transesterified, with a softening point of 74°C. The present invention improves the light resistance of a synthetic resin by adding a homopolymer or copolymer represented by the general formula () or () to the synthetic resin. 5
Parts by weight, preferably 0.01 to 3 parts by weight. Examples of synthetic resins to be improved in light resistance in the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, ethylene-vinyl acetate copolymers, and ethylene-propylene copolymers. polyolefins and their copolymers, such as polymers,
Polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer Polymer, 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, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-
Acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, petroleum resins, coumaron resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) ), acrylonitrile-butadiene-styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl Formal, polyvinyl butyral, linear polyester, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, or phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. be able to.
Furthermore, rubbers such as isoprene rubber, butadiene rubber, allylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. Also included are crosslinked polymers such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed polymers such as expanded polystyrene foamed with a foaming agent. Oxidative stability can be improved by further adding a phenolic antioxidant to the composition of the present invention. Examples of these 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-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3'・5'-di-tert-butyl-4'-hydroxybenzylthio)-1,3,5-triazine, 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), 2,2'-methylenebis[6-(1-methylcyclohexyl) p-cresol], bis[3,5-bis(4-hydroxy-3 -tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-
Methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,3,5-tris( 3.
5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 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-hydroxy-3,5-di-tertiary
butyl) phenoxy-1,3,5-triazine,
Phenols such as 4,4'-thiobis(6-tert-butyl-m-cresol) and carbonic acid oligoesters of 4,4'-butylidenebis(2-tert-butyl-5-methylphenol) (for example, polymerization degree 2,
Examples include polyhydric phenol carbonate oligoesters such as 3, 4, 5, 6, 7, 8, 9, 10, etc.). It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability. Examples of these sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl (e.g., glycerin). , trimethylolethane, trimethylolpropane, pentaerythritol,
trishydroxyethyl isocyanurate) (eg, pentaerythritol tetralauryl thiopropionate). By further adding a phosphorus-containing compound such as phosphite to the composition of the present invention, light resistance and heat resistance can be improved. Examples of the phosphorus-containing compound include trioctyl phosphite,
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-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl)bis[4,4'-butylidene bis(3- Methyl-6-tert-butylphenol)], 1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol, pentaerythritol diphosphite, tris[4,4'-isopropylidene bis( 2-tert-butylphenol)] phosphite, phenyl diidecyl phosphite, di(nonylphenyl)pentaerythritol diphosphite, tris(1,3-di-stearoyloxyisopropyl)phosphite, 4,4'-isopropylidene bis( 2-tert-butylphenol) di(nonylphenyl) phosphite, 9.
Examples include 10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite. By adding other light stabilizers to the compositions of the invention, their lightfastness can be further improved. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,
Hydroxybenzophenones such as 2,2'-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3'-t-butyl-5'- methylphenyl)
-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-di-t-butylphenyl)-
Benzotriazoles such as 5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-di-t-amylphenyl)benzotriazole, Benzoates such as phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2'- Thiobis(4-t-octylphenol) Ni salt, [2,2′-thiobis(4-
t-octylphenolate)]nn-butylamine
Ni, nickel compounds such as (3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, α-cyano-β-methyl-β-(p-methoxyphenyl)acrylic acid Substituted acrylonitriles such as methyl, N-2-ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalate diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalate diamide, etc. Examples include oxalic acid dianilides. In addition, if necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, an organotin compound,
Plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, lubricants, processing aids, and the like can be included. Next, the present invention will be specifically explained using examples. However, the present invention is not limited to these examples. Example 1 Polyvinyl chloride 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Trisnonylphenyl phosphite 0.2 Ca-stearate 1.0 parts by weight Zn-stearate 0.1 Stabilizer (Table 3) 0.3 The above formulation was rolled on a roll. A sheet with a thickness of 1 mm was prepared by kneading the mixture. Using this sheet, a light resistance test was conducted in a weatherometer. The result is the third
Shown in the table.

【table】

[Table] Example 2 Polypropylene 100 parts by weight Stearyl-β-3,5-di-tert-butyl-4-
Hydroxyphenylpropionate 0.2 Stabilizer (Table 4) 0.3 A press sheet with a thickness of 0.3 mm was prepared using the above formulation, and a light resistance test was conducted using a high-pressure mercury lamp. A light resistance test was also conducted on the sheet after it had been immersed in hot water at 80°C for 15 hours. The results are shown in Table 4.

【table】

[Table] Example 3 Ethylene-vinyl acetate copolymer 100 parts by weight 2,6-di-tert-butyl-p-cresol 0.1 Ca-stearate 0.1 Zn-stearate 0.1 Diisodecyl phenyl phosphite 0.2 Stabilizer (Table 5) ) 0.2 The above mixture was kneaded on a roll at 130°C, and then a press sheet (thickness: 0.4 mm) was prepared at 140°C. After irradiating this sheet for 1000 hours, the residual elongation rate was measured in a weatherometer. The results are shown in Table 5.

【table】

[Table] Example 4 Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3-(3.5-di-3
Butyl-4-hydroxyphenyl)propionate] methane 0.1 Distearylthiodipropionate 0.3 Stabilizer (Table 6) 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 ABS resin 100 parts by weight 4.4'-butylidene bis(2-tert-butyl-m-
Cresol) 0.1 Stabilizer (Table 7) 0.3 Extrude the above compound and injection mold it to a thickness of 2 mm.
A test piece was made. Using this sheet, the residual tensile strength after 100 hours of irradiation was measured using a weatherometer. The results are shown in Table 7.

[Table] Example 6 It is known that ordinary stabilizers volatilize during high-temperature processing of resins, and their effects are significantly lost after decomposition. In this example, the effect of high-temperature processing was confirmed by repeatedly performing extrusion processing. After mixing the resin and additives in a mixer for 5 minutes according to the following formulation, a compound was prepared using an extruder. After extrusion was repeated five times (cylinder temperature: 230°C, 240°C, head die temperature: 250°C, rotation speed: 20 rpm), a test piece was made using an injection molding machine using this compound. (Cylinder temperature
240° C., nozzle temperature 250° C., injection pressure 475 Kg/cm ² ) Using the obtained test piece, a light resistance test was conducted using a high-pressure mercury lamp. In addition, the same test was conducted for a sample that had been extruded once. The results are shown in Table 8. <Composition> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 parts by weight Stearyl-β-3,5-di-tert-butyl-4-
Hydroxyphenylpropionate 0.1 Dilaurylthiodipropionate 0.2 Stabilizer (Table 8) 0.2

[Table] Example 7 Polyurethane resin (Asahi Denka U-100) 100 parts by weight Ba-stearate 0.7 Zn-stearate 0.3 2,6-di-tert-butyl-p-cresol 0.1 Stabilizer (Table 9) 0.3 Knead the above blend on a roll at 70°C for 5 minutes,
A sheet with a thickness of 0.5 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. The results are shown in Table 9.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A homopolymer of a substituted piperidine compound represented by the following formula () or (), or a compound containing at least one double bond that can be polymerized with this homopolymer, based on 100 parts by weight of a synthetic resin. copolymer with
A stabilized synthetic resin composition containing 0.001 to 5 parts by weight. (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, R ₅ represents a hydrogen atom or an acyl group, and R ₆ represents a hydrogen atom, an oxyl group, an alkyl group, and a substituted alkyl group. group, R ₇ represents a hydrogen atom or a methyl group, X represents an alkylene group, Y represents an alkantriyl group, and n is 0
Or indicates 1. )