JPH021186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized synthetic resin composition,
More specifically, the present invention relates to a synthetic resin composition with improved photostability, which contains a maleic acid (or fumaric acid) ester/α-olefin copolymer having a polyalkylpiperidyl group. polyethylene, polypropylene, ABC 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 biperidine compounds have the characteristics of being non-coloring themselves and acting as quenchers rather than UV absorbers. It is receiving particular attention. 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 blooms. 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. However, when these polymers are used, although the volatility of the stabilizer is reduced, their stabilizing effect is not sufficient, and they are also poor in compatibility with the polymeric substance being stabilized, causing bloom etc. It had some shortcomings and needed further improvement. As a result of intensive studies in view of the current situation, the present inventors have found that all of the above drawbacks can be overcome by using a maleic acid (or fumaric acid) ester/α-olefin copolymer having a polyalkylpiperidyl group. This discovery led to the present invention. That is, the present invention contains 0.001 to 5 polymer parts of a copolymer having a molecular weight of 1,000 to 20,000 and having a repeating unit represented by the following general formula () and a repeating unit represented by the general formula () per 100 polymer parts of the synthetic resin. The present invention provides a synthetic resin composition comprising the following: [In the formula, R ₁ and R ₂ are each an alkyl group,

[expression] or

[Formula] is shown. X is

[expression] or

[Formula] is shown, and R ₆ represents a lower alkyl group. R ₂ represents a hydrogen atom or an alkyl group. R ₄ represents an alkylene group. R ₅ represents a hydrogen atom or a methyl group. Y is CH ₂ , C=O, CH—OH or

[Formula] is shown, and R ₇ represents an alkylene group. However, in all of the repeating units represented by the general formula (), R ₁ and R ₂ do not simultaneously represent an alkyl group. ] [In the formula, R ₈ represents a hydrogen atom or an alkyl group. ] Hereinafter, the compounds used in the present invention will be explained in detail. The alkyl groups represented by R ₁ and R ₂ include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl,
Examples include tetradecyl, hexatecyl, and octadecyl. Examples of the alkyl group represented by R ₃ include benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2,3-epoxypropyl, and the like, in addition to the above-mentioned alkyl groups. Examples of the alkylene group represented by R ₄ include ethylene, 1,2-propylene, and 1,2-butylene. Examples of the lower alkyl group represented by R ₆ include methyl, hydroxymethyl, ethyl, propyl, butyl and the like. Examples of the alkylene group represented by R ₇ include 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, 1,2-octadecylene, 2-methyl-2-
Examples include hydroxymethyl-1,3-propylene and 2-ethyl-2-hydroxymethyl-1,3-propylene. The alkyl group represented by R ₈ is methyl,
ethyl, butyl, hexyl, octyl, decyl,
dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl,
Hexacosyl, octacosyl, triacontyl,
1 or more carbon atoms such as tetracontyl, pentacontyl, etc.
There are 50 straight or branched chains. The maleic acid (or fumaric acid) ester/α-olefin copolymer used in the present invention is
For example, maleic acid (or fumaric acid) ester having a polyalkylpiperidyl group and α-olefin are polymerized using a conventional polymerization initiator such as an organic peroxide or an azonitrile compound, or maleic acid (or fumaric acid) It can be easily produced by a transesterification reaction between a dialkyl ester/α-olefin copolymer and an alcohol having a polyalkylpiperidyl group. In this case, the molar ratio of maleate ester to α-olefin may be selected from the range of 1:1 to 10 to 10:1, preferably 1:1 to 5:1. Furthermore, the copolymer used in the present invention is a copolymer of maleic acid (or fumaric acid) ester and α-olefin, but this is further copolymerized with a small proportion of other copolymerizable monomers. It may also be a copolymer. Other monomers include styrene, acrylic esters, methacrylic esters, and the like. Hereinafter, the present invention will be explained in more detail using specific synthesis examples, but the present invention is not limited by these examples. Synthesis Example 1 Bis(9-aza-3-ethyl-8,8,9,
10,10-pentamethyl-1,5-dioxaspiro[5,5]udecylmethyl)malate 3.25g
(0.005 mol), 1-dodecene 0.84 g (0.005 mol)
was dissolved in 10 ml of benzene, 0.08 g of azobisisobutyronitrile was added, and the mixture was heated at 100°C under a nitrogen stream for 36 hours.
The mixture was heated and stirred for hours. After distilling off the solvent, it was dried at 160°C and 1 mmHg for 6 hours, and then cooled to obtain a copolymer (stabilizer No.
1) 3.5g was obtained. As a result of analysis of the product, the N content was 3.47% (calculated value 3.42
%) and a molecular weight of 3200. The maleic acid ester/α-olefin copolymer shown in the following table was synthesized by the same operation as in Synthesis Example 1.

[Table] Synthesis example 2 PAR-124 (Me) (manufactured by Mitsubishi Kasei; dimethyl maleate/dialene 124 alternating copolymer, molecular weight
3200) 3.3g, 2,2,6,6-tetramethyl-
1-Hydroxyethyl-unit-4-one 2.0
g and 0.05 g of lithium amide to pseudocumene 30
ml 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 pale yellow viscous liquid (stabilizer No. 5). As a result of analyzing the product, the molecular weight was 4800, and the N content was
It was found that about 50% of the methyl ester of PAR-124(Me) was transesterified. In the same manner as in Synthesis Example 2, a transesterified product of a maleic acid dialkyl ester/α-olefin copolymer with a piperidine compound as shown in the following table was produced.

[Table] In the present invention, the maleic acid (or fumaric acid) ester/α-olefin copolymer is added to a synthetic resin to improve its light resistance, and the amount added is usually 100 parts of the polymer. 0.001 to 5 polymerized parts, preferably 0.01 to 3 polymerized parts. 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 ester-butadiene-styrene copolymer, methacrylic 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, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-
Rubbers such as butadiene copolymer rubber or 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-
Phenols such as (tertiary butyl) phenoxy-1,3,5-triazine, 4,4'-thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (2-tert-butyl-5 -methylphenol) carbonate oligoester (for example, degree of polymerization 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 alkylpropionic acids such as butyl, octyl, lauryl, and stearyl (e.g., glycerin). , trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetraurylthiopropionate). 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, distearyl pentaerythritol diphosphite, tetra (tridecyl)-1,
1,3-tris(2-methyl-5-tert-butyl-
4-hydroxyphenyl)butane diphosphite, tetra( _C12-15 mixed alkyl)-4,4'-isopropylidene diphenylphosphite, 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'-isopropylene Lyden diphenol polyphosphite bis(octyl phenyl) 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 diisodecyl phosphite,
Di(nonylphenyl)pentaerythritol diphosphite, tris(1,3-di-stearoyloxyisopropyl)phosphite, 4,4'-isopropylidene bis(2-tert-butylphenol) di(nonylphenyl)phosphite, 9,
10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(2,4-di-tert-butylphenyl)-4,4'-
Examples include 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)-5
-benzotriazoles such as chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-5'-di-t-amylphenyl)benzotriazole; enyl salicylate, pt-
Butylphenyl salicylate, 2,4-di-t-
Butylphenyl-3,5-di-t-butyl-4-
Benzoates such as hydroxybenzoate,
2,2'-thiobis(4-t-octylphenol) Ni salt, [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine Ni, (3,
5-di-t-butyl-4-hydroxybenzyl)
Nickel compounds such as phosphonic acid monoethyl ester Ni salt, α-cyano-β-methyl-β-(p
-Methoxyphenyl) substituted acrylonitriles such as methyl acrylate and N-2-ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalamide, N-2-ethylphenyl-
Examples include oxalic acid dianilides such as N'-2-ethoxyphenyl oxalic acid diamide. In addition, if necessary, the composition of the present invention may contain a polymerizable deactivator, a nucleating agent, a metallic 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 Zn-stearate 0.1 Sample (Table 1) 0.3 The above mixture was kneaded on a roll A sheet with a thickness of 1 mm was prepared. Using this sheet, a light resistance test was conducted in a weatherometer. The results are shown in Table-1.

【table】

[Table] Example 2 Polypropylene 100 parts by weight Stearyl-β-3,5-di-tert-butyl-4
-Hydroxyphenylproonate 0.2 Sample (Table 2) 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-2.

[Table] Example 3 Ethylene-vinyl acetate polymer 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 Sample (Table 3) 0.2 After kneading the above mixture on a roll at 130℃, press sheet (thickness 0.4mm) was made at 140℃. did. The residual tensile strength of this sheet was measured after 500 hours of irradiation in a weatherometer. The results are shown in Table-3.

[Table] Example 4 Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Methane 0.1 Distearylthiodipropionate 0.3 Test Material (Table 4) 0.2 The above blend was pressed in a kneading machine to make 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 4.

【table】

[Table] Example 5 ABS resin 100 parts by weight 4,4'-butylidene bis(2-tert-butyl-m
-Cresol) 0.1 Sample (Table-5) 0.3 Roll knead the above mixture and press it to a thickness of 3 mm.
I made a sheet. Using this sheet, the residual tensile strength after 800 hours of irradiation was measured using a weatherometer. The results are shown in Table-5.

[Table] Example 6 It is known that ordinary stabilizers lose their effectiveness significantly due to volatilization, decomposition, etc. during high-temperature processing of resins. 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-6. <Composition> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 Stearyl-β-3,5-di-tert-butyl-4
-Hydroxyphenylpropinate 0.1 Dilaurylthiodipropionate 0.2 Sample (Table 6) 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 Sample (Table 7) 0.3 The above mixture was kneaded on a roll at 70℃ 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 rate after 30 hours of irradiation was measured using this sheet and a fade meter. The results are shown in Table-7.

【table】

【table】

Claims (1)

[Claims] 1. The following general formula () for 100 parts by weight of synthetic resin:
A synthetic resin composition containing 0.001 to 5 parts by weight of a copolymer with a molecular weight of 1,000 to 20,000 having a repeating unit represented by the formula () and a repeating unit represented by the general formula (). [In the formula, R ₁ and R ₂ are each an alkyl group, [Formula] or [Formula], X represents [Formula] or [Formula], and R ₆ represents a lower alkyl group. R ₃ represents a hydrogen atom or an alkyl group. R ₄ represents an alkylene group. R ₅ represents a hydrogen atom or a methyl group. Y represents CH ₂ , C═O, CH—OH or [Formula], and R ₇ represents an alkylene group. However, in all of the repeating units represented by the general formula (), R ₁ and R ₂ do not simultaneously represent an alkyl group. ] [In the formula, R ₃ represents a hydrogen atom or an alkyl group. ]