JPH0670187B2 - Polymeric material composition with improved photostability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymer material composition containing a high-molecular weight benzotriazole compound, more specifically, 2- (2-hydroxy-3-allyl-5). The present invention relates to a polymer material composition having improved photostability by adding a copolymer of a -substituted phenyl) benzotriazole compound and an α, β-unsaturated carboxylic acid compound.

[Conventional technology and its problems]

It is known that polymer materials such as polypropylene, polyvinyl chloride, and styrene resins are deteriorated by the action of light and cause discoloration or reduction in mechanical strength, and cannot withstand long-term use.

Therefore, in order to prevent deterioration of the polymer material due to this light, various stabilizers have been conventionally used, and 2-hydroxyphenylbenzotriazoles are light stabilizers having a relatively large stabilizing effect. Are known.

However, the conventionally used benzotriazole compound has a drawback that it is easily volatilized during the processing of a polymer material or is easily extracted by water or an organic solvent, and is not practically satisfactory.

For this reason, it has been proposed to use a (co) polymer of a benzotriazole compound having an acryloyl group in the molecule, but these compounds are not only complicated in synthesis method, but also the benzotriazole compound is removed by hydrolysis. It has a defect that it separates, and it is not yet satisfactory.

[Means for solving problems]

DISCLOSURE OF THE INVENTION The present invention has been earnestly studied in order to obtain a compound having excellent photostabilization effect on a polymer material and excellent heat resistance, water resistance, and solvent resistance. As a result, a repeating unit represented by the following general formula (I) is shown. And, it was found that a copolymer having a repeating unit represented by the following general formula (II) solves all of the above problems and, when added to a polymer material, significantly improves the photostability of the polymer material, Arrived

That is, in the present invention, the repeating unit represented by the following general formula (I) and the repeating unit represented by the following general formula (II) are added to 100 parts by weight of the polymer material in a molar ratio of 1:50 to 50: 1. The present invention provides a polymeric material composition having improved light stability, which comprises 0.001 to 5 parts by weight of a copolymer having a molecular weight of 500 to 50,000 contained in the above ratio.

(In the formula, R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents an alkyl group or an aralkyl group.) (In the formula, R ₅ represents a hydrogen atom, an alkyl group or -CO-X ₁ -R ₈ , and R ₆ represents -CO-X ₁ -R ₈ or R ₇ represents a hydrogen atom, an alkyl group, -CO-X ₁ -R ₈ or -CH ₂ -CO-X ₁ -R ₈ , and R ₅ and R ₆ together represent May be indicated. X ₁ and X ₂ are each -0- or -N (R ₉ )-
R ₈ and R ₉ are each a hydrogen atom, an alkyl group or And Z is -CH or R ₁₀ represents a hydrogen atom or an alkyl group, and R ₁₁ represents an alkyl group. ) Hereinafter, the polymer material composition of the present invention will be described in detail.

In the copolymer used in the present invention, R ₂ , R ₅ ,
Examples of the alkyl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, amyl, sec-amyl, hexyl and heptyl. , Octyl, 2-ethylhexyl, tertiary octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, cyclopentyl, cyclohexyl,
Ciurooctyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and the like, R ₂
Examples of the aralkyl group represented by are benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like.

In the copolymer used in the present invention, the monomer providing the repeating unit represented by the general formula (I) is
Formula (Ia) [In the formula, R ₁ and R ₂ are the same as those in the general formula (I), and R ₃ and R ₄ are hydrogen atoms. ] The specific example is 2- (2
-Hydroxy-3-allyl-4-methylphenyl) benzotriazole, 2- (2-hydroxy-3-allyl-
5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-allyl-5-methylphenyl) -5-methylbenzotriazole, 2- (2-
Hydroxy-3-allyl-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3-allyl-5-octylphenyl) benzotriazole, 2
-(2-Hydroxy-3-allyl-5-cumylphenyl) benzotriazole, 2- (2-hydroxy-3-)
Examples include tert-butyl-5-allylphenyl) benzotriazole and the like.

These monomers are known compounds as described in JP-B-41-19179, and are easily produced by back-packing a 2-hydroxyphenylbenzotriazole compound and an allyl halide compound and then transferring them. obtain.

Further, the monomer giving the repeating unit represented by the general formula (II) is represented by the formula (IIa) [In the formula, R ₅ , R ₆ and R ₇ are the same as those in the general formula (II). ) Is an α, β-unsaturated mono-polycarboxylic acid and its ester, amide, imide or anhydride, and specific examples of the α, β-unsaturated carboxylic acid include acrylic acid and methacrylic acid. , Isocrotonic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, 1-butene-2,3,4-tricarboxylic acid and the like can be mentioned, and as the ester, the α, β-unsaturated carboxylic acid methyl or ethyl can be used. , Propyl, butyl, octyl, dodecyl-ester and other alkyl esters and 2,2,
6,6-Tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, 9-aza-3-ethyl-8,
8,10,10-Tetramethyl-1,5-dioxaspiro [5,5]
Examples thereof include esters having a piperidine ring such as -3-undecylmethyl-ester, and examples of the amide include α, β-unsaturated carboxylic acid methylamide, butyramide, dibutylamide, octylamide, and third octylamide. Alkyl amide and 2,2,6,6-tetramethyl-4-piperidyl amide, N-butyl-N- (2,2,6,6
-Tetramethyl-4-piperidyl) amide and the like having an amide having a tetramethylpiperidyl group, and examples of the imide include maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide, N-2,2,6,6.
-Tetramethyl-4-piperidyl maleimide and the like.

The copolymer having the repeating units represented by the general formulas (I) and (II) used in the present invention has a benzotriazole monomer represented by the general formula (Ia) and an α represented by the general formula (IIa). , Β-unsaturated carboxylic acid derivative is polymerized using a usual polymerization initiator such as an organic peroxide or an azonitrile compound, and then, if necessary,
It can be easily produced by esterification or amide formation.

In this case, the molar ratio of the monomer represented by the general formula (Ia) to the monomer represented by the general formula (IIa) is preferably 1:50 to 50: 1, more preferably 1:20 to 20. : 1 selected from the range. When the ratio of the monomer represented by the general formula (Ia) (the ratio of the reversion unit represented by the general formula (I)) is less than 1:50, it is added to obtain a desired stabilizing effect. If the amount of the desired copolymer is too large, and if the above ratio exceeds 50: 1, it becomes difficult to proceed with the copolymerization to obtain the copolymer.

Further, in producing the copolymer used in the present invention, a smaller proportion of styrene, alkyl vinyl ether,
Other copolymerizable monomers such as vinyl acetate may be copolymerized.

The copolymer used in the present invention has a molecular weight of 50.
If it is less than 0, the heat resistance of the copolymer itself is poor, and it tends to volatilize under processing conditions, and if it exceeds 50,000, the compatibility with the polymer material deteriorates.

Hereinafter, the present invention will be described in more detail by showing synthetic examples of the copolymer used in the present invention, but the present invention is not limited by these synthetic examples.

Synthesis Example 1 Synthesis of 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole / maleic anhydride copolymer 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole 26.5 g (0.1 mol), maleic anhydride 9.8 g (0.1 mol) and azobis (isobutyronitrile) 3.63 g were dissolved in xylene 80 ml, and the mixture was stirred at 80 ° C. under nitrogen flow for 1 hour.
Stir for 5 hours.

After desolvation under reduced pressure, the product was triturated in ethanol to obtain a white solid product (Copolymer-1).

This product has a softening point of 240 to 260 ° C. and a molecular weight of about 2500, and as a result of infrared spectroscopic analysis, an absorption based on an acid anhydride is 1850.
cm ^-1, the 1780 cm ^-1 and 920 cm ^-1, absorption based on benzotriazole located respectively 1560 cm ^-1 and 750 cm ^-1, also 1
The absorption due to the double bond at 640 cm ^-1 had disappeared, and it was confirmed that the product was the desired product.

Synthesis Example 2 Synthesis of 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole / dibutyl maleate copolymer by esterification of Copolymer-1 Copolymer-1 obtained in Synthesis Example 1 10 g, n-butanol 15 g and paratoluene sulfonic acid 0.5 g were dissolved in xylene and refluxed for 6 hours under a nitrogen stream while removing water.

After washing with water and drying, a trace amount of insoluble matter was filtered off, the filtrate was desolvated, and then triturated in ethanol to obtain a white powder product (Copolymer-2).

This product has a softening point of 290 to 300 ° C. and a molecular weight of about 3000. As a result of infrared spectroscopic analysis, an absorption based on ester is 1720.
Located cm ^-1, also 1850 cm ^-1, which disappeared absorption based on acid anhydride 1780 cm ^-1 and 920 cm ^-1, it was confirmed that it was the desired product.

Synthesis Example 3 Synthesis of 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole / dibutyl maleate copolymer 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole 5.3 g (0.02 mol), 2.35 g (0.024 mol) of maleic anhydride and 0.38 g of di-tert-butyl peroxide were dissolved in 10 ml of xylene.
Stir for hours. Then di-tert-butyl peroxide 0.
19 g and maleic anhydride 0.2 g (0.002 mol) were added, and the mixture was further stirred at the same temperature for 18 hours.

Then, 0.2 g of paratoluenesulfonic acid and 5 g of n-butanol were added, and the mixture was stirred under reflux for 6 hours while removing water.

After washing with water and drying, a trace amount of insoluble matter was filtered off and the filtrate was desolvated to obtain a slightly yellow glassy solid product (Copolymer-3).

The product has a softening point of 50-60 ° C. and a molecular weight of about 3500,
Infrared spectroscopic analysis showed an ester-based absorption of 1720 cm ^-1
In addition, the absorption based on benzotriazole is 1560 cm ^-1 and 75
There each 0 cm ^-1, also have disappeared absorption based on the double bond of 1640 cm ^-1, it was confirmed that it was the desired product.

Synthesis Examples 4 to 7 Copolymers (copolymers-4 to 7) having the molecular weights shown in the following table were produced in the same manner as in Synthesis Example 3 except that the type of alcohol used for esterification was changed as shown in the table below.

Synthesis Example 8 Synthesis of 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole / di-2-methylhexylmalate copolymer 2- (2-hydroxy-3-allyl-5-methylphenyl) ) Benzotriazole 10.6 g (0.04 mol), di-2-
Ethylhexyl malate (13.6 g, 0.04 mol) and tert-butyl peroxide (2.4 g) were dissolved in xylene, and the mixture was stirred at 125 ° C. for 30 hours under a nitrogen stream.

Then, the mixture was stirred under reflux for 3 hours, and desolvated under reduced pressure to obtain a pale yellow liquid product (copolymer-8) having a molecular weight of about 2000.

Synthesis Example 9 Synthesis of 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole / butyl methacrylate copolymer 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole 26.5 g (0.1 mol), 14.2 g (0.1 mol) of butyl methacrylate and 0.4 g of azobisisobutyronitrile were dissolved in 40 ml of benzene, and the mixture was stirred under a nitrogen stream at reflux temperature for 12 hours.

This solution was poured into a large amount of ethanol, and the formed precipitate was filtered off to obtain a white solid product (Copolymer-9) having a softening point of 250 ° C. or higher and a molecular weight of about 20,000.

Synthetic Examples 10 to 19 The copolymers having the molecular weights shown in the following table (Copolymer-10) were prepared in the same manner as in Synthetic Example 4 or Synthetic Example 5 except that the kinds and molar ratios of the monomers used in the synthesis of the copolymers were changed as shown in the following table. ~
19) were manufactured respectively.

In the present invention, a copolymer having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) is added to a polymer material to improve its stability, particularly light stability. The amount of addition is usually 0.001 to 5 parts by weight, preferably 0.
01 to 3 parts by weight. If the addition amount is less than 0.001 part by weight, the stabilizing effect is poor, and if the addition amount exceeds 5 parts by weight, the improvement in the stabilizing effect commensurate with the addition amount is not recognized.

Examples of the polymer material for which stability is to be improved in the present invention include, for example, α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, ethylene-vinyl acetate copolymers, and ethylene-propylene copolymers. Polyolefins such as polymers and copolymers thereof, 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, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride -Styrene-maleic anhydride terpolymer, salt Vinyl-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Vinyl-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resin such as internally plasticized polyvinyl chloride, Petroleum resin, coumarone resin,
Polystyrene, polyvinyl acetate, acrylic resin, polyacrylonitrile, copolymer of styrene or α-methylstyrene and other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, Acrylic ester-budadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, methacrylate resin such as polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terebutarate, polybutylene terephthalate, etc. Chain polyester, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, fibrin resin, or phenol resin, urea resin, melamine resin, Carboxymethyl resins, unsaturated polyester resins, and silicone resins. Furthermore,
Isoprene rubber, butadiene rubber, acrylonitrile-
Rubbers such as butadiene copolymer rubber and styrene-butadiene copolymer rubber, and blends of these resins may be used. Further, a cross-linked polymer such as cross-linked polyethylene cross-linked by peroxide or radiation and a foamed polymer such as expanded polystyrene foamed by a foaming agent are also included.

By further adding a phenolic antioxidant to the composition of the present invention, its oxidative stability can be further improved. As the phenolic antioxidant, for example, 2,
6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octoxyphenol, stearyl- (3,5-di-methyl-4-hydroxybenzyl) thioglycolate, steaallyl-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) benzyl malonate, triethylene glycol bis (3-tert-butyl-4-hydroxy) -5-methylphenylpropionate), 3,9-bis [1,1-dimethyl-2
-(3-tert-Butyl-4-hydroxy-5-methylphenylpropionyloxy) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (4-methyl-6) -Tert-butylphenol), bis [3,
5-bis (4-hydroxy-3-tert-butylphenyl)
Butyric acid] glycol ester, 4,4′-butylidene bis (6-tert-butyl-m-cresol), 2,
2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2 'ethylidene bis (4-tert-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) phenoxy-1,3,5-triacine, 4,4'-thiobis (6-tertiary
Butyl-m-cresol) and the like.

It is also possible to improve the oxidative stability of the composition of the present invention by adding a sulfur-based antioxidant. Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl-, and butyl-, octyl-, lauryl, stearyl-.
And alkyl thiopropionic acid polyhydric alcohols (eg, 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, its light resistance and heat resistance can be further improved. Examples of the phosphorus-containing compound include trioctyl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, and tris (2,4
-Di-tert-butylphenyl) phosphite, triphenylphosphite, tris (mono-dimixed nonylwenyl) phosphite, tris (nonylphenyl) phosphite, distearin pentaerythritol diphosphite, hexa (tridecyl) -1,1 , 3- tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetra (C ₁₂ ~ ₁₅ mixed alkyl) -
4,4'-isopropylidene diphenyl diphosphite,
Tetra (tridecyl) -4,4'-butylidene bis (3-
Methyl-6-tert-butylphenol) diphosphite,
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, di (nonylphenyl) pentaerythritol diphosphite, 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'-
Biphenylene diphosphonite and the like can be mentioned.

The light resistance can be further improved by adding another light stabilizer to the composition of the present invention. Examples of the light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Such as hydroxybenzophenones, 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-amylphenyl) benzotriazole, phenyl salicylate, p-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxy Benzoate, hexadecyl-3,5-di-t-
Benzoates such as butyl-4-hydroxybenzoate, 2,2'-thiobis (4-t-octylphenol) N
i salt, [2,2′-thiobis (4-t-octylphenolate)]-n-butylamine Ni, (3,5-di-t-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, etc. Nickel compounds, substituted acrylonitriles such as methyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate, N-2-ethylphenyl-
Oxanic acid dianilides such as N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, and 2,2,6,6- Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-
4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5
-Di-tert-butyl-4-hydroxybenzyl) malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 , 6,6-Tetramethyl-4-piperidyl) ・ di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ・Di (tridecyl) -1,2,3,4-butane tetracarboxylate, N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine / dimethyl succinate condensate, 2-tertiary octyl Amino-4,6-dichlorotriazine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane / 1,2
-Dibromoethane condensate, 2,2,4,4-tetramethyl-7
-Oxa-3,20-diazadisspiro [5.1.11.2] heneicosan-21-one, 3,9-bis [1,1-dimethyl-2-tris (2,2,6,6, -tetramethyl-4-piperidyl (Oxycarbonyl) butylcarbonyloxyethyl] -2,4,8,
10-Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2-tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxyethyl]- 2,4,8,10-Tetraoxaspiro (5.
5] Undecane, 1,3,8-triaza-3-dodecyl-8-
Acetyl-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione, 1,5,8,12-tetrakis [4,6-bis [N
Examples thereof include hindered amine compounds such as -butyl-N- (2,2,6,6, -tetramethyl-4-piperidyl) amino] -1,3,5-triazin-2-yl] dodecane.

In addition, if necessary, the composition of the present invention includes a heavy metal deactivator, a nucleating agent, a metallic soap, an organic tin compound, a plasticizer, an epoxy compound, a pigment, a filler, a foaming agent, an antistatic agent, a flame retardant. , A lubricant, a processing aid and the like can be included.

The polymeric materials stabilized according to the invention can be used in a great variety of forms, for example as films, fibers, tapes, sheets, various moldings, and also in paints, binders for lacquers, adhesives, putties and photographic materials. It can also be used as a base.

〔Example〕

Next, the present invention will be specifically described with reference to examples. However, the invention is not limited to these examples.

Example 1 <Compounding> Polypropylene 100 parts by weight Calcium stearate 0.2 Pentaerythritol tetrakis (3,5-di-tert-butyl-
4-Hydroxyphenylpropionate) 0.1 Stabilizer (See Table 1 below) 0.2 A press sheet having a thickness of 0.3 mm was prepared with the above composition, and this sheet was subjected to a light resistance test using a high pressure mercury lamp. A light resistance test was also conducted on the sheet after being immersed in hot water at 80 ° C for 48 hours. The results are shown in Table 1 below.

Example 2 In order to see the effect when a hindered amine light stabilizer was further used in combination with the composition of the present invention, a sheet was prepared in the same manner as in Example 1 with the following formulation.

Using this sheet, a light resistance test using a high pressure mercury lamp was performed. The results are shown in Table 2 below.

<Compounding> Polypropylene 100 parts by weight Calcium stearate 0.2 Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenylpropionate) 0.1 Copolymer-3 0.1 Hindered amine light stabilizer 0.1 (See Table 2 below) ) Example 3 It is known that ordinary stabilizers lose their effects remarkably due to volatilization, decomposition and the like during high temperature processing of resins.

In this example, the effect of high temperature processing was confirmed by repeating extrusion processing.

Resin and additives were mixed with a mixer for 5 minutes according to the following formulation, and then compound was prepared with an extruder (cylinder temperature 230 ° C, 240 ° C, head die temperature 250 ° C, rotation speed 20r
pm). After extrusion was repeated 5 times, a test piece was prepared using this compound with an injection molding machine (cylinder temperature 240 ° C., nozzle temperature 250 ° C., injection pressure 475 kg / cm ² ).

A light resistance test was conducted using a high pressure mercury lamp using the obtained test piece. Further, the same test was performed for the one-time extrusion. The results are shown in Table 3 below.

<Blend> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 Stearyl-β-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 Dilaurylthiodipropionate 0.2 Stabilizer (Table 3 below) Refer) 0.2 Example 4 <Compounding> Polyethylene 100 parts by weight Calcium stearate 1.0 Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 0.1 Distearylthiodipropionate 0.3 Stabilizer (see below) (See Table-4) 0.2 The above mixture was kneaded and then pressed to form a sheet having a thickness of 0.5 mm. Using this sheet, the light resistance was measured in a weatherometer, and the time until embrittlement was measured. The results are shown in Table 4 below.

Example 5 <Composition> Parts by weight Polyvinyl chloride (Vinica 37H) 100 Di-2-ethylhexyl phthalate 45 Tricresyl phosphate 5 Epoxy resin (Epicoat 828) 3 Barium stearate 0.3 Barium nonylphenate 0.3 Zinc stearate 0.6 Octyl Diphenylphosphite 0.5 Sorbitan monopalmitate 2.0 Methylenebisstearylamide 0.3 Stabilizer (see Table 5 below) 0.1 With the above composition, a film having a thickness of 0.1 mm was prepared with a kneading roll. Using this film, a weather resistance test was carried out in a weatherometer. The results are shown in Table 5 below.

Example 6 <Compounding> ABS resin 100 parts by weight 4,4'-butylidene bis (2-tertiary butyl-m-cresol) 0.1 Stabilizer (see Table 6 below) 0.25 The above composition was roll-kneaded and pressed to a thickness. I made a 3mm sheet. Use this sheet in a weatherometer
The tensile strength residual ratio after irradiation for 800 hours was measured. The results are shown in Table 6 below.

Example 7 <Compounding> Polyurethane resin 100 parts by weight (U-100 manufactured by Asahi Denka Co., Ltd.) Barium stearate 0.7 Zinc stearate 0.3 2,6-Di-tert-butyl-p-cresol 0.1 Stabilizer (see Table 7 below) 0.5 The above composition was kneaded on a roll at 70 ° C. for 5 minutes and pressed at 120 ° C. for 5 minutes to prepare a sheet having a thickness of 0.5 mm. Using this sheet, the elongation residual ratio after irradiation for 50 hours was measured with a fade meter. The results are shown in Table 7 below.

Example 8 The stabilizer component (copolymer) of the present invention is also useful as a light stabilizer for coatings. In this example, the results were examined for a two-layer metallic luster paint comprising a base coat containing a metallic pigment and a transparent top coat.

a) Base coat paint 100 g of methyl methacrylate, 66 g of n-butyl acrylate,
Take 30 g of 2-hydroxyethyl methacrylate, 4 g of methacrylic acid, 80 g of xylene and 20 g of n-butanol, and add 110
2 g of azobisisobutyronitrile with heating and stirring at ℃,
A solution consisting of 0.5 g of dodecyl mercaptan, 80 g of xylene and 20 g of n-butanol was added dropwise over 3 hours. Then, the mixture was stirred at the same temperature for 2 hours to prepare an acrylic resin solution having a resin solid content of 50%.

12 parts by weight of the acrylic resin solution, 2.5 parts by weight of butoxylated methylol melamine (manufactured by Mitsui Toatsu Co., Ltd .; Uvanine 20SE60; resin solid content 60%), 50 parts by weight of cellulose acetate butyrate resin (20% butyl acetate solution), aluminum pigment (Toyo Aluminum Co., Ltd .; Alpaste 1123N) 5.5 parts by weight, xylene 10 parts by weight, butyl acetate 20 parts by weight and copper phthalocyanine nimble-0.2 parts by weight were taken as a base coat paint.

b) Topcoat paint 48 parts by weight of the acrylic resin solution, 10 parts by weight of butoxylated methylol melamine, 10 parts by weight of xylene, 4 parts by weight of butyl glycol acetate and a stabilizer (see Table 8 below).
15 parts by weight (0.5% based on the solid content) was taken as a top coat paint.

A base coat paint was sprayed onto a primer-treated copper plate so that the dry film thickness was 20 μ, and after standing for 10 minutes, the top coat paint was sprayed so that the dry film thickness was 30 μ.
After leaving it for 15 minutes, it was baked at 140 ° C for 30 minutes to obtain a test piece.

The test piece was put in a weatherometer and the time until the crack of the coating film was generated was measured. The results are shown in Table 8 below.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08F 220/36 MMQ 7242-4J 220/60 MNH 7242-4J

Claims (1)

[Claims] 1. A repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) are added to 100 parts by weight of a polymeric material in a molar ratio of 1:50 to 50: 1. A polymer material composition having improved light stability, comprising 0.001 to 5 parts by weight of a copolymer having a molecular weight of 500 to 50,000 contained in proportion. (In the formula, R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents an alkyl group or an aralkyl group.) (In the formula, R ₅ represents a hydrogen atom, an alkyl group or -CO-X ₁ -R ₈ , and R ₆ represents -CO-X ₁ -R ₈ or R ₇ is a hydrogen atom, an alkyl group, -CO-X ₁ -R ₈ or-
CO ₂ -CO-X ₁ -R ₈ is shown, and R ₅ and R ₆ are jointly May be indicated. X ₁ and X ₂ each represent -0- or -N (R ₉ )-, and R ₈ and R ₉
Are each a hydrogen atom, an alkyl group or And Z is -CH or R ₁₀ represents a hydrogen atom or an alkyl group, and R ₁₁ represents an alkyl group. )