JPH0218346B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin composition stabilized against the effects of light, and more particularly, to a synthetic resin composition that is stabilized against the effects of light.
The present invention relates to a synthetic resin composition having improved light resistance by containing a high molecular weight compound having a 2,6,6-tetramethylpiperidyl group and a 2-hydroxybenzophenon-4-yl group. 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 have special effects and have attracted particular attention in recent years. Also, 2-
Hydroxyphenylbenzotriazoles and 2
-Hydroxybenzophenones are useful light stabilizers that act as UV absorbers, and it is also known that when used in combination with hindered piperidine light stabilizers, a complementary stabilizing effect can be obtained. ing. In recent years, attempts have been made to combine an ultraviolet absorbing group and a hindered piperidine group into the same molecule. For example, JP-A-55-49355 proposes a molecular bond of benzotriazole or 2-hydroxybenzophenone and polyalkylpiperidine. However, this compound has insufficient photostabilizing ability, and since it is a relatively low molecular weight compound, it has drawbacks such as volatilization during high-temperature processing of polymers and extraction by water or organic solvents. , which was unsatisfactory in practical terms. The present inventors conducted intensive studies to find compounds with excellent photostabilizing ability and good volatility and water resistance. As a result, N-2,3-epoxypropylpiperidines and 2,4-di- The present invention was completed based on the discovery that polycarbonate, polyester or polyurethane derivatives of adducts with hydroxybenzophenones or 2,4-hydroxybenzotriazoles have good performance. That is, the present invention provides a stabilized synthetic resin composition obtained by adding 0.001 to 10 parts by weight of a compound represented by the following general formula () to 100 parts by weight of a synthetic resin. (In the formula, X is CH-O-,

[expression] or

[Formula] is shown, and Y represents a carbonyl group, a diacyl group or a dicarbamoyl group. A is a hydrogen atom, an acyl group, or R ₃ -O-Y
- indicates. B is -O- _R3 , shows. Z is

[expression] or

[Formula] is shown. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom.
R ₂ represents a lower alkyl group. R ₃ represents an alkyl group or an aryl group. n represents 1 to 30. ) The compound represented by the general formula () used in the present invention will be described in detail below. The alkyl group represented by R ₁ is methyl,
Ethyl, propyl, isopropyl, butyl, tertiary
Examples include butyl, hexyl, octyl, nonyl, dodecyl, octadecyl, etc., and halogen atoms include chlorine, bromine, and iodine. Examples of the lower alkyl group represented by R ₂ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and sec-butyl.
Alkyl groups represented by _R3 include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl,
Nonyl, decyl, dodecyl, tetradecyl, octadecyl, benzyl, phenethyl, cyclohexyl, methoxyethyl, ethoxyethyl, butoxyethyl, methoxyethoxyethyl, butoxyethyl, etc., and the aryl group includes phenyl,
Tolyl, xylyl, tertiary butylphenyl, ditertiary
Examples include butylphenyl, octylphenyl, nonylphenyl, and the like. Examples of the acyl group represented by A include the following acyl groups derived from carboxylic acids. That is,
Formic acid, acetic acid, propionic acid, butyric acid, pivalic acid,
Octylic acid, lauric acid, palmitic acid, stearic acid, acrylic acid, crotonic acid, oleic acid,
Acetoacetic acid, levulinic acid, biruvic acid, ketostearic acid, aminoacetic acid, dodecylmercaptopropionic acid, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, benzoic acid, toluic acid, 4-tert-butyl Benzoic acid, 3,5-di-tertiary
Butyl-4-hydroxybenzoic acid, nicotinic acid,
Examples include acyl groups derived from isonicotinic acid and 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid. The diacyl group represented by Y is oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid,
Sebacic acid, dodecanniic acid, eicosanniic acid, tartaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, iminodiacetic acid, thiodipropionic acid, diglycolic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, thiophenedicarboxylic acid, Examples include diacyl groups derived from furandicarboxylic acid and dicarboxyethylpiperazine, and dicarbamoyl groups include diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, phenyl diisocyanate, tolylene diisocyanate, diphenyl ether diisocyanate, and xylene diisocyanate. Carbamoyl derived from divalent isocyanates such as diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, bis(isocyanatomethyl)cyclohexane, and 3-(2'-isocyanatocyclohexyl)propyl isocyanate. The basics are given. Therefore, the general formula () used in the present invention
Examples of the compound represented by the formula include those shown in Table 1 below. In addition, in the table

【formula】 teeth

[Formula] is shown. The compound represented by the general formula () used in the present invention is, for example,

A formula obtained by reacting a compound represented by [Formula] with 2,4-dihydroxybenzophenones or 2,4-dihydroxyphenylbenzotriazoles

It can be easily produced by reacting the glycol represented by the formula with a dicarboxylic acid or its lower alkyl ester, diisocyanates, or carbonic diesters. Next, specific synthesis examples of the compounds used in the present invention will be described, but the present invention is not limited by these synthesis examples. Synthesis example Table 1, Synthesis of No. 1 compound 2,4-dihydroxybenzophenone 4.32g,
1-(2,3-epoxypropyl)-2,2,6,
6-tetramethyl-4-hydroxypiperidine
4.26g, 1.07N potassium t-butoxide
- 1.5 g of butanol solution and 80 ml of pseudocumene
The mixture was heated under reflux for 7 hours. After washing with water and drying, insoluble materials were separated and the mixture was left in a refrigerator overnight to obtain a yellow powder product. As a result of elemental analysis and infrared spectroscopy, 2-hydroxy-4-[2-hydroxy-3-
It was confirmed to be (2,2,6,6-tetramethyl-4-hydroxypiperidin-1-yl)]propoxybenzophenone. 1.72g of the above compound, 0.70g of diethyl succinate,
0.05 g of tetraisopropyl titanate and 10 ml of pseudocumene were taken and heated under reflux for 7 hours under a nitrogen stream. The resulting pale brown precipitate was separated and dried to obtain a pale yellow powder product with a softening point of 170-205°C. Molecular weight: Approximately 4000 IR 1595cm ^-1 , 1610cm ^-1 , 1725cm ^-1 The present invention improves the light resistance of a synthetic resin by adding the compound represented by the general formula () above, and the amount added is usually , 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight per 100 parts by weight of synthetic resin.
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, 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, 2,6-diphenyl-4-octadecyloxyphenol, 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-tertiary)
butylphenol), 2,2'-methylenebis[6
-(1-methylcyclohexyl)p-cresol], bis[3,5-bis(4-hydroxy-3
-tert-butylphenyl) butylidene acid] glycol ester, 4,4'-butylidene bis(6-
tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidene bis(4-sec-butyl-6-
tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-
Methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 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-tert-butyl) ) Phenols such as phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol) and 4,4'-butylidenebis(2
- tert-butyl-5-methylphenol) carbonate oligoester (e.g. polymerization degree 2, 3, 4, 5,
Examples include polyhydric phenol carbonate oligoesters such as 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. These sulfur-based antioxidants include, for example, dialkylthiodipropionates such as dilauryl, dimyristyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl. 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, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, di Stearyl 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 diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(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, bis(2,4,-di-tert-butylphenyl)penta Erythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris[4,4'-isopropylidene bis(2
-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonyl phenyl) 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 -phosphenanthrene-10-oxide, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, and the like. 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, Phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-
Benzoates such as di-t-butyl-4-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)phosphonic acid monoethyl ester
Nickel compounds such as Ni salts, α-cyano-β-
Substituted acrylonitriles such as methyl-β-(p-methoxyphenyl)acrylate, N-2-
Ethyl phenyl-N'-2-ethoxy-5-tertiary
Oxalic acid dianilides such as butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetra(2,
2,6,6-tetramethyl-4-piperidyl)butanetetracarboxylate, bis(1,2,
2,6,6-pentamethyl-4-piperidyl)-
3,5-di-tert-butyl-4-hydroxybenzyl-n-butyl malonate, tertiary octylamine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene Diamine/cyanuric chloride condensate, dimethyl succinate/1
-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine condensate,
Examples include piperidine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl)-pentaerythritol diphosphite. 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 Polypropylene 100 parts by weight Stearyl-β-3,5-di-tert-butyl-4-
Hydroxyphenylpropionate 0.2 Stabilizer (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. Table 2 shows the results.
Shown below.

[Table] Example 2 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-3. <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 (Sample Table 3) 0.2

[Table] Example 3 Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3-(3,5-di-tertiary)
Butyl-4-hydroxyphenyl) propionate] methane 0.1 Distearyl thiodipropionate 0.3 Stabilizer (sample Table 4) 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 4.

【table】

[Table] Example 4 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 (sample Table-5) 0.2 After kneading the above mixture on a roll at 130℃, press sheet (thickness 0.4mm) at 140℃ Created. The residual tensile strength of this sheet was measured after 500 hours of irradiation in a weatherometer. The results are shown in Table-5.

【table】

[Table] Example 5 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 Stabilizer (sample Table-6) 0.3 The above formulation The mixture was kneaded on a roll to form a sheet with a thickness of 1 mm. Using this sheet, a light resistance test was conducted in a weatherometer. Table the results.
6.

[Table] Example 6 ABS resin 100 parts by weight 4,4'-butylidene bis(2-tert-butyl-m-
Cresol) 0.1 Stabilizer (Sample Table 7) 0.3 Roll knead the above mixture and press it to a thickness of 3 mm.
A sheet was created. Using this sheet, the residual tensile strength after 800 hours of irradiation was measured using a weatherometer. The results are shown in Table-7.

[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 (Sample Table 8) 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 of this sheet was measured using a fade meter after 30 hours of irradiation. Table 8 shows the results.
Shown below.

[Table] Example 8 The compounds of the present invention are also useful as light stabilizers for paints. In this example, the effect of a two-layer metallic luster paint consisting of a base coat containing a metallic pigment and a transparent top coat was examined. (a) Base coat paint Methyl methacrylate 100g, acrylic acid n-
Take 66 g of butyl, 30 g of 2-hydroxyethyl methacrylate, 4 g of methacrylic acid, 80 g of xylene, and 20 g of n-butanol, heat to 110°C while stirring, and add 2 g of azobisisobutyronitrile.
A solution of 0.5 g of dodecyl mercaptan, 80 g of xylene and 20 g of n-butanol was added dropwise over 3 hours. After that, stir at the same temperature for 2 hours, and remove the resin solids.
A 50% acrylic resin solution was prepared. 12 parts by weight of the above acrylic resin, butoxylated methylolmelamine (manufactured by Mitsui Toatsu Co., Ltd.; Yuban)
20SE60; resin solid content 60%) 2.5 parts by weight, cellulose acetate butyrate resin (20% butyl acetate solution) 50 parts by weight, aluminum pigment (manufactured by Toyo Aluminum Co., Ltd.; Alpaste 1123N) 5.5 parts by weight, xylene 10 parts by weight, 20 parts by weight of butyl acetate and 0.2 parts by weight of copper phthalocyanine blue were used as a base coat paint. (b) Top coat paint 48 parts by weight of the above acrylic resin, 10 parts by weight of butoxylated methylolmelamine, 10 parts by weight of xylene,
4 parts by weight of butyl glycol acetate and 0.15 parts by weight (0.5% based on solid content) of a sample compound were taken to prepare a top coat paint. Dry film thickness of base coat paint on primer treated steel plate is 20μ
After standing for 10 minutes, top coat paint was sprayed to give a dry film thickness of 30 μm. After allowing it to stand for 15 minutes, it was baked at 140°C for 30 minutes to obtain a specimen. The above sample was placed in a weatherometer and the time until cracking of the coating film appeared was measured. The results are shown in Table-9.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A stabilized synthetic resin composition obtained by adding 0.001 to 10 parts by weight of a compound represented by the following general formula () to 100 parts by weight of a synthetic resin. (In the formula, X is CH-O-,
[Formula] or [Formula], and Y represents a carbonyl group, a diacyl group, or a dicarbamoyl group. A is a hydrogen atom, an acyl group, or R ₃ -O-Y
- indicates. B is -O- _R3 , shows. Z represents [formula] or [formula]. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom.
R ₂ represents a lower alkyl group. R ₃ represents an alkyl group or an aryl group. n represents 1 to 30. )