JPH0218345B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to synthetic resin compositions stabilized against the effects of light, more particularly 2,2,6,6-
The present invention relates to a synthetic resin composition that has improved light resistance by containing a triazine compound containing a tetramethylpiperidine-4-spiroketal group. Synthetic resins such as polyethylene, polypropylene, and polyvinyl chloride are generally sensitive to the effects of light, and are known to deteriorate due to the effects of light, causing discoloration or a decrease in mechanical strength, and not being able to withstand long-term use. ing. Therefore, in order to prevent the deterioration of synthetic resins due to this light, various stabilizers have been used in the past.
The stabilizing effect of conventionally used light stabilizers is still insufficient, and the stabilizers themselves are unstable to heat or oxidation, or are easily extracted from the resin by solvents such as water. In addition, many of these compounds color the resin, which makes it impossible to stabilize synthetic resins over a long period of time. Among these conventionally used light stabilizers, piperidine-based compounds have attracted particular attention in recent years because they are non-coloring in themselves and act as quenchers rather than UV absorbers. ing. However, conventionally known piperidine-based compounds have insufficient photostabilizing ability and also have the disadvantage that they are easily extracted from the resin by water. Furthermore, these piperidine-based compounds themselves have insufficient heat resistance, and when processing synthetic resins at high temperatures, they often decompose or volatilize and lose their effectiveness. Among these piperidine-based compounds, compounds containing a triazine ring have advantages such as the compound itself has relatively good heat resistance, the inexpensive cyanuric chloride can be used as a raw material, and the reaction is easy. have. Examples of piperidine compounds containing a triazine ring include JP-A-49-21389, JP-A-52-71486, JP-A-52-73886, JP-A-53-9782, and JP-A-53.
−67749, JP-A No. 106483, JP-A-54-
No. 126249, JP-A-55-98180, JP-A-55-
No. 102637, JP-A-55-104279, JP-A-56-4639
Various compounds have been proposed in Japanese Patent Application Laid-open No. 56-30974. However, all of the compounds described in these publications are derived from 4-hydroxy or 4-amino-piperidines, and their photostabilizing ability and heat resistance of the compounds themselves are not satisfactory. , further improvements were requested. In view of the current situation, the present inventors have conducted extensive studies and found that the compound represented by the following general formula () has excellent photostabilizing ability, and the heat resistance of the compound itself is also extremely good. I found it. 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, R ₁ represents a hydrogen atom, oxyl or an alkyl group, R ₂ represents a lower alkyl group, R ₃ ,
R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a lower alkyl group. A is

[Formula] R ₉ -O-,

[expression] or

[Formula] is shown. R ₇ and R ₈ are each a hydrogen atom, an alkyl group, or

[Formula], R ₉ is an alkyl group, an aryl group, or

[Formula] is shown. B is hydrogen atom or

[Formula] is shown. n represents 1 to 20. ) Why does the compound represented by the above general formula () used in the present invention include the 4-hydroxy or 4-
Although it is not yet clear whether it has superior photostabilizing ability compared to compounds derived from aminopiperidines, the compound used in the present invention is a spiroketal compound derived from a polyhydric alcohol having a neopentyl structure. It is assumed that one of the reasons for this is that the heat resistance of the compound itself has been significantly improved. Hereinafter, the compounds used in the present invention will be explained in more detail. The alkyl group represented by R ₁ is methyl,
Ethyl, propyl, butyl, isobutyl, sec-butyl, tertiary-butyl, hexyl, heptyl, octyl, dodecyl, benzyl, hydroxymethyl, 2
-hydroxyethyl, 2-hydroxypropyl,
Examples include 2,3-dihydroxypropyl, 2-hydroxybutyl, 2-hydroxyoctyl, acetoxyethyl, propionylethyl, octyloylethyl, 2,3-epoxypropyl, and the like. Examples of the lower alkyl group represented by R ₂ , R ₃ , R ₄ , R ₅ and R ₆ include methyl, ethyl, propyl, butyl and the like. As the alkyl group represented by R ₇ and R ₈ ,
Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, tertiary octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, hydroxymethyl, hydroxyethyl, methoxymethyl, methoxy Examples include ethyl, butoxyethyl, dimethylaminopropyl, and the like. The alkyl group represented by R ₉ is methyl,
ethyl, butyl, amyl, hexyl, octyl,
Examples include 2-ethylhexyl, decyl, isodecyl, dodecyl, tridecyl, tetradecyl, octadecyl, methoxyethyl, ethoxyethyl, butoxyethyl, and aryl groups include phenyl, tolyl, xylyl, tert-butylphenyl, octylphenyl, nonylphenyl, etc. can give. Representative examples of the compounds represented by the general formula () used in the present invention are shown in Table 1 below. In the table,

【ceremony

[Formula] is shown. The compound represented by the general formula () used in the present invention can be obtained by, for example, reacting cyanuric chloride with piperidines, and then reacting this with a 2,2,6,6-tetramethylpiperidine-4-spiroketal alcohol compound. It can be easily produced by reaction. Alternatively, cyanuric chloride and 2,2,6,6-tetramethylpiperidine-4-
It can also be easily produced by reacting a spiroketal alcohol compound and then reacting it with a piperidine. The present invention will be explained in more detail below using specific synthesis examples, but the present invention is not limited by the following synthesis examples. Synthesis example 1 (A) N,N'-bis(4,6-dichloro-1,3,
Preparation of 5-triazin-2-yl)piperazine 12.9 g of anhydrous piperazine was dissolved in 80 ml of acetone and cooled to 0-5°C. To this, add 1 ml of a solution of 55.3 g of cyanuric chloride dissolved in 300 ml of acetone.
The mixture was added dropwise over a period of time, and after the completion of the addition, the mixture was stirred at 0 to 5°C for 1 hour. Add 12g of sodium hydroxide to 80g of water.
ml was added dropwise at the same temperature for 1 hour.
The mixture was further stirred for 4 hours. 150 ml of water was added, separated, washed with water, and dried to obtain a white powder product with a melting point of 300°C or higher. (B) N,N'-bis[4,6-bis(9-aza-
3-ethyl-8,8,10,10-tetramethyl-
1,5-dioxaspiro[5.5]-3-undecylmethoxy)-1,3,5-triazine-2-
Production of 9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]-
3-Undecylmethanol 27.1g to toluene
Dissolve in 100ml, add 3.5g of NaH, and heat to 80-100℃
The mixture was stirred for 1 hour. To this, 8.3 g of N,N'-bis(4,6-dichloro-1,3,5-triazin-2-yl)piperazine was gradually added,
The mixture was stirred for 12 hours under refluxing toluene. The reaction solution was filtered through Celite while hot, washed with water, dried, and the solvent was removed to obtain 20 g of a white powder product. The product was recrystallized from benzene to obtain the desired product as a white powder with a melting point of 229°C. Synthesis Example 2 N,N'-bis[4,6-bis(9-aza-3
-Ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]-3-undecylmethoxy)-1,3,5-triazine-2
-yl]piperazine (Table 1, No. 3 compound) 9-aza-3-ethyl-8,8,9,10,10-
Pentamethyl-1,5-dioxaspiro[5.5]-
6.3 g of 3-undecylmethanol, N,N'-bis(4,6-dichloro-1,3,5-triazine-
Take 1.9 g of 2-yl) piperazine, 1.2 g of powdered sodium hydroxide, and 40 ml of toluene, and add under nitrogen stream.
Refluxed for 20 hours. Kyoward 700 after washing and drying
(adsorbent manufactured by Kyowa Chemical) to remove the solvent. Add 50ml of n-hexane to the residue to obtain a white powder product.
1.5g was obtained. The product was recrystallized from benzene/hexane to obtain the desired product as a white powder with a melting point of 220°C. The present invention improves the light resistance of a synthetic resin by adding the compound represented by the general formula () to the synthetic resin. is 0.01~3
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, chroman 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, 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)pentaerythritol Diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris[4,4'-isopropylidene bis(2
-tertiary 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)acrylics and N-2
Examples thereof include oxalic acid dianilides such as -ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide. 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 (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】

[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 (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 Distearylthiodipropionate 0.3 Stabilizer (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] 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 (Table 5) 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-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 (Table 6) 0.3 Roll the above formulation A sheet with a thickness of 1 mm was prepared by kneading the mixture above. Using this sheet, a light resistance test was conducted in a weatherometer. Table the results.
6.

【table】

[Table] Example 6 ABS resin 100 parts by weight 4,4'-butylidene bis(2-tert-butyl-m-
Cresol) 0.1 Stabilizer (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 (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】

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, R ₁ represents a hydrogen atom, oxyl or an alkyl group, R ₂ represents a lower alkyl group, R ₃ ,
R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a lower alkyl group. A represents [Formula] R ₉ -O-, [Formula] or [Formula]. R ₇ and R ₈ each represent a hydrogen atom, an alkyl group, or [Formula], and R ₉ represents an alkyl group, an aryl group, or [Formula]. B represents a hydrogen atom or [Formula]. n represents 1 to 20. )