JPS62181360A - High polymer material composition having improved light stability - Google Patents

Abstract

PURPOSE:A high polymer material composition having improved light stability, obtained by blending a high polymer material with a copolymer of a specific benzotriazole monomer and an alpha,beta-unsaturated carboxylic acid compound. CONSTITUTION:A composition obtained by blending 100pts.wt. high polymer material with 0.001-5pts.wt. copolymer which is obtained by polymerizing a 2-(2-hydroxy-3-allyl-5-substituted phenyl)benzotriazole compound with an alpha,beta-unsaturated carboxylic acid compound by the use of an organic peroxide, etc., and has a repeating unit shown by formula I (R1 is H, halogen or alkyl; R2 is alkyl or aralkyl; R3 and R4 are H or alkyl) and a repeating unit shown by formula II (R5 is H, alkyl or group shown by formula III; R6 is group shown by formula III or formula IV; R7 is H, alkyl, group shown by formula III or formula V; R5 and R6 may be bonded to form group shown by formula VI; X1 and X2 are O or group shown by formula VII; R8 and R9 are H, alkyl, etc.,) and 500-50,000mol.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polymeric material composition prepared by adding a high molecular weight hensitriazole compound, specifically, 2-(2-hydroxy-3-allyl-5 The present invention relates to a polymeric material composition with 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 deteriorate due to the action of light, causing discoloration or a decrease in mechanical strength, and thus cannot withstand long-term use.

Therefore, in order to prevent the deterioration of polymeric materials due to this light, various stabilizers have been used in the past, and 2-hydroxyphenylbenzotriazoles are known to be light stabilizers with a relatively large stabilizing effect. Are known.

However, the hensitriazole compounds conventionally used have the disadvantage that they tend to volatilize during processing of polymeric materials or are easily extracted by water or organic solvents, and are not practically satisfactory.

For this reason, it has been proposed to use (co)polymers of hensitriazoles having an acryloyl group in the molecule, but not only are the synthesis methods of these compounds complicated, but the benzotriazole compounds are eliminated by hydrolysis. However, it has the disadvantage of causing separation, and has not yet been satisfactory.

[Means for solving problems]

The present inventor has an excellent photostabilizing effect on polymeric materials,
Moreover, as a result of intensive studies to obtain a compound with good heat resistance, water resistance, and solvent resistance, we found that the repeating unit represented by the following general formula (+) and the repeating unit represented by the following general formula (n) were The present inventors have discovered that a copolymer having the above-mentioned compound solves all of the above problems and, when added to a polymeric material, significantly improves the photostability of the polymeric material, and has thus arrived at the present invention.

That is, the present invention provides 100 parts by weight of a polymeric material with a repeating unit represented by the following general formula (()) and the following general formula (II
) having a repeating unit represented by a molecular weight of 500 to 50
．． The present invention provides a polymeric material composition with improved photostability, which contains 0.001 to 5 parts by weight of 000NO:+Ho'Jmer.

(In the formula, R1 represents a hydrogen atom, a halogen atom, or an alkyl group, R2 represents an alkyl group or an aralkyl group, and R
3 and R4 each represent a hydrogen atom or an alkyl group. ) (wherein, R2 is a hydrogen atom, an alkyl group, or Co
R@, Rh represents -Co X+ Rs or CHCHz Co X+ Rs, Co
X+ R++ R1 is a hydrogen atom, an alkyl group, -CO-X + R
s or -CHz Co
L) h represents an oxyl, alkyl group or an acyl group, and R1 represents an alkyl group. ] The polymer material composition of the present invention will be described in detail below.

In the copolymer used in the present invention, R+,
RtlRx, Ra, R5, R? , Re, Rq, R+. The alkyl group represented by R1 is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary-butyl,
Butyl, amyl, 37th mil, hexyl, heptyl, octyl, 2-ethylhexyl, tertiary octyl, nonyl,
Examples include decyl, dodecyl, tetradecyl, octadecyl, etc., and examples of the aralkyl group represented by R2 include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and the like.

In addition, as the acyl group represented by R6゜, formyl,
acetyl, propionyl, butyroyl, acryloyl,
Examples include benzoyl.

In the copolymer used in the present invention, the heptamer providing the repeating unit represented by the general formula (I) is:
In the formula (Ia) C, R+, Rz, R3 and R4 are the same as in the general formula (I). ], and a specific example is 2-(2
-Hydroxy-3-allyl-4-methylphenyl)hencytriazole, 2-(2-hydroxy-3-allyl-
5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-methallyl-5-methylphenyl)hencytriazole, 2-(2-hydroxy-
3-allyl-5-methylphenyl)-5-methylhensitriazole, 2-(2-hydroxy-3-allyl-5
-tert-butylphenyl)benzotriazole, 2-(2
-Hydroxy-3-allyl-5-tertiary octylphenyl)benzotriazole, 2-(2-hydroxy-3-
Allyl-5-cumylphenyl)hencytriazole, 2
-(2-hydroxy-3-tert-butyl-5-allylphenyl)benzotriazole and the like.

These monomers are known compounds as described in Japanese Patent Publication No. 41-19179, and can be easily produced by combining a 2-hydroxyphenylbenzotriazole compound and an allyl halide compound and then transferring them. obtain.

Further, the monomer providing the repeating unit represented by the general formula (II) is represented by the formula (Ila) R.

α,β-unsaturated mono-polycarbonyl I'l represented by
and its esters, amides, imides, or anhydrides. Specific examples of the α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Examples of the esters include methyl, ethyl, propyl, butyl, octyl,
Alkyl esters such as dodecyl-ester and 2,2°6.6-tetramethyl-4-piperidyl, 1.2°2.
6.6-bentamethyl-4-piperidyl, 9-7zar3
-ethyl-8,8,10,10-tetramethyl-1,5
-dioxaspiro(5,5)-3-undecylmethyl-
Examples of the amides include esters having a piperidine ring such as esters, and examples of the amides include alkylamides of the α,β-unsaturated carboxylic acids such as methylamide, butylamide, dibutylamide, octylamide, and tertiary octylamide; Amides having a tetramethylpiperidyl group such as 6.6-tetramethyl-4-piperidylamide, N-butyl-N-(2,2,6゜6-tetramethyl-4-piperidyl)amide, and imide Examples include maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide, N-2,2,6,6-tetramethyl-4-piperidylmaleimide, and the like.

The copolymer having repeating units represented by the general formulas (I) and (■) used in the present invention has the general formula (I) and (■).
The hendztriadur monomer represented by I a) and the α, β-unsaturated carboxylic acid derivative represented by the general formula (Ha) are mixed with a conventional polymerization initiator such as an organic peroxide or an azonitrile compound. It can be easily produced by polymerizing the compound using a compound, followed by esterification or amide conversion, if necessary.

In this case, the molar ratio of the monomer represented by the general formula (!a) to the monomer represented by the general formula (Ha) is preferably 1:50 to 50:1, more preferably 1:20.
-20:l.

In addition, when producing the copolymer used in the present invention, a small proportion of styrene, alkyl vinyl ether,
Other copolymerizable monomers such as vinyl acetate may also be copolymerized.

The copolymer used in the present invention has a molecular weight of 5
If it is less than 00, the copolymer itself has poor heat resistance,
It tends to swell under processing conditions, and if it exceeds 5o, oo, or o, it becomes less compatible with polymeric materials.

The present invention will be explained in further detail by showing synthesis examples of the copolymer used in the present invention below, but the present invention is not limited by these synthesis examples.

Synthesis Example 1 2-(2-hydroxy-3-allyl-5-methylphenyl)benzotriazole 26.5 g (0.1 mol)
, 9.8 g (0.1 mol) of maleic anhydride and 3.63 g of azobis(isobutyronitrile) were added to 80 ml of xylene.
and stirred at 80° C. for 15 hours under a nitrogen stream.

After removing the solvent under reduced pressure, the mixture was ground in ethanol to obtain a white solid product (copolymer-1).

This product has a softening point of 240-260°C and a molecular weight of about 25
00, and as a result of infrared spectroscopy, the absorption based on acid anhydride is 1850 cm-', 1780 cm-' and 92
At 0 cm-', the absorption based on benzotriazole is 15
There are 60co+-' and 750cm+-' respectively,
In addition, the absorption based on the double bond at 1640 cm-' disappeared, confirming that it was the desired product.

Synthesis Example 2 110 g of copolymer obtained in Synthesis Example 1, 1 n-butanol
5 g and 0.5 g of para-toluenesulfonic acid were dissolved in xylene and refluxed for 6 hours under a nitrogen stream while removing water.

After washing with water and drying, the slightly agitated insoluble matter was filtered off, and the filtrate was desolvented and ground in ethanol to obtain a white powder product (copolymer-2).

This product has a softening point of 290-300°C and a molecular weight of about 30
00, and as a result of infrared spectroscopy, the absorption based on ester was found at 1120 cm-', and 1850 ca+-'
, 1780 cm-' and 920 cm-' based on the acid anhydride (absorption disappeared, confirming that it was the target product.

Synthesis Example 3 2-(2-hydroxy-3-allyl-5-methylphenyl)benzotriazole J 115.3 g (0.02 mol), maleic anhydride 2.35 g (0.024 mol) and di-tertiary 0.38 g of butyl peroxide was dissolved in 10 ml of xylene and stirred at 125° C. for 18 hours under a nitrogen stream. Then di-tert-butyl peroxide 0.19
g and 0.2 g (0.002 mol) of maleic anhydride were added thereto, and the mixture was further stirred at the same temperature for 18 hours.

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

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

This product has a softening point of 50-60°C and a molecular weight of about 3500.
As a result of infrared spectroscopy, there is an absorption based on ester at 1720 cm-1, an absorption based on benzotriazole at 1560 cm-' and 750 cffi-', and an absorption based on a double bond at 1640 cm-1. It had disappeared, confirming that it was the object.

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

Synthesis Example 8 2-(2-hydroxy-3-allyl-5-methylphenyl)benzotriazole lo, 6 g (0.04 mol),
Di-2-ethylhexyl malate 13°6g (0.04
mol) and di-tert-butyl peroxide (2.4 g) were dissolved in xylene and stirred at 125° C. for 30 hours under a nitrogen stream.

Thereafter, the mixture was stirred under reflux for 3 hours, and the solvent was removed under reduced pressure to obtain a pale yellow liquid product (copolymer-8) with a molecular weight of about 2,000.

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

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

Synthesis Examples 10 to 19 Copolymers with the molecular weights shown in the table below (Copolymer-10
~19) were produced, respectively.

(Continuation of the previous table) The present invention improves the stability of a polymer material by adding a copolymer having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) to a polymer material. In particular, it improves photostability, and the amount added is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the polymeric material.

Examples of polymeric materials whose stability is to be improved 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 such as polymers and their copolymers, 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-trimaleic anhydride Original copolymer, m-conversion and nyl-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chloride and nyl-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 copolymer, internal plasticization Halogen-containing synthetic resins such as polyvinyl chloride, petroleum resins, coumaron resins, polystyrene, polyvinyl acetate, acrylic resins, polyacrylonitrile, styrene or α-methylstyrene 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 Linear polyesters such as formal, polyvinyl butyral, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polyamide,
Examples include polycarbonate, polyacetal, polyurethane, cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Furthermore, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. Also included are crosslinked polymers such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed polymers such as expanded polystyrene foamed with a foaming agent.

By further adding a phenolic antioxidant to the composition of the present invention, its oxidative stability can be further improved. As this phenolic antioxidant, for example, 2
．． 6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octoxyphenol, stearyl-(3
, 5-di-methyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5
-di-tert-butyl phenyl) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, 2,4.6-) soot (3', 5"
-tert-butyl-4-hydroxyhensylthio)l,
3.5. - triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate,
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-6-37'thylphenol), bis[3,5
-bis(4-hydroxy-3-tert-butylphenyl)butyrin acid coglycol ester, 4,4°-butylidenebis(6-tert-butyl-m-cresol), 2°2°-ethylidenebis(4,6- (di-tert-butylphenol), 2,2"-ethylidene bis(4-tert-butyl-
6-tert-butylphenol), ■.

1.3-) Lis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis(2-i3butyl-4
-Methyl-6-(2-hydroxy-3-tert-phthyl-5-methylhensyl)phenyl]terephthalate, 1,
3.5-) Lis(2゜6-dimethyl-3-hydroxy-
4-tert-butyl)hensyl isocyanurate, 1.3.
5-tris(3,5-di-tert-butyl-4-hydroquinbenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3-(3,5-di-tert.]ethyl-4
-Hydroxyphenyl)propionate comethane, 1,
3.5-4-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-
Examples include di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol), and the like.

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 the sulfur-based antioxidant include dilauryl,
Dialkyl thiodipropionates such as similystyl, distearyl, and butyl, octyl-5 lauryl
, alkylthiopropionic acid polyhydric alcohols such as stearyl (e.g. glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (eg pentaerythritol tetralauryl thioprobionate).

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, tris(2,4
-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (mono-di mixed nonylphenyl) phosphite, tris (nonylphenyl) phosphite, distearin pentaerythritol diphosphite, hexa(tridecyl)-1,1° 3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite, tetra(C+ t~1. mixed alkyl)-4,4''-isopropylidene diphenyl diphosphite, tetra(tridecyl) -4,4'-Butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, bis(octylphenyl) ・Bis[4,4°-butylidenebis(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-dihydro-9-oxa-1O-
Phosphaphenanthrene-IO-oxide, tetrakis(2,4-di-tert-butylphenyl)-4,4'-
Examples include biphenylene diphosphonite.

By adding other light stabilizers to the compositions of the invention, their lightfastness can be further improved. 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. Hydroxyhensiphenones such as 2-(2°-hydroxy-3°-t-butyl-5°-ethylphenyl)-
5-chlorohencytriazole, 2-(2°-hydroxy-3", 5°-di-t-butylphenyl)-5-chlorohencytriazole, 2-(2"-hydroxy-5
°-Methylphenyl)hencytriazole, 2-(2'
-Hydroxy-3"5"-di-t-amylphenyl)
Benzotriazoles such as benzotriazole, phenyl salisolate, p-L-butylphenyl salyl-
t, 2.4-di-1-butyl phenyl-3.5-no L
-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-butyl-4-hydroxybenzoate, etc., 2゜2゜-thiobis(4-L
-octylphenol) N1 salt, [2,2°-thiobis(4-t-octylphenolate)]-]n-butylamine Ni, (3°5-di-t-)゛thyl-4-hydronitoshenzyl) Phosphonic acid monoethyl ester Ni
Nickel compounds such as salts, α-cyano-β-methyl-β
Substituted acrylonitriles such as -(p-methoxyphenyl)methyl acrylate, N-2-ethylphenyl-N"
-2-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, etc., and 2,2,6,6-tetra Methyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-
piperidyl) sebacate, bis(I,2,2,6,6-
Bentamethyl-4-piperidyl) sebacate, bis(I
,2,2,6,6-bentamethyl-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(I,2,2,6,6-bentamethyl-4-piperidyl) di(tridecyl) )-1,2゜3.4-butanetetracarboxylate, N-hydroxyethyl-2,
2,6,6-tetramethyl-4-hydroxypiperidine/dimethyl succinate condensate, 2-tertiary octylamino-
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-diazadispiro(5,1,11
,2) Heneicosan-21-one, 3.9-bis[1
, l-dimethyl-2-tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxyethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 3.9-Bis [1゜1
-dimethyl-2-tris(I,2,2,6,6-bankmethyl-4-piperidyloxycarbonyl)butylcarbonyloxyethyl)-2,4°8.10-tetraoxaspiro(5,53 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-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amine)-1,3,5-)riazine- 2-yl] Hindered amine compounds such as dodecane are mentioned.

In addition, as necessary, the composition of the present invention may include a polymerization group deactivator, a nucleating agent, a metal soap, a tin compound, a plasticizer, an epoxy compound, a pigment, a filler, a blowing agent, an antistatic agent, Flame retardants, lubricants, processing aids, etc. can be included.

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

C Example] Next, the present invention will be specifically explained with reference to Examples.

However, the present invention is not limited to these examples.

Example 1 Blend> Polypropylene 100 Parts by weight Calcium stearate 0.2 Stabilizer (see Table 1 below) 0.2 A press sheet with a thickness of 0.31 mm was prepared using the above blend, and this sheet was subjected to high pressure. A light resistance test was conducted using a mercury lamp. In addition, a light resistance test was also conducted on the sheet after being soaked in hot water at 80° C. for 48 hours. The results are shown in Table 1 below.

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

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

Blend> Polypropylene 100 parts by weight Calcium stearate 0.2 Copolymer-30,1 Table 2 (continued from Table 2) Example 3 Ordinary stabilizers evaporate and decompose during high-temperature processing of resin, resulting in their effects being reduced. is known to be significantly lost.

In this example, the influence of high temperature processing was confirmed by repeatedly performing extrusion processing.

After combining the resin and additives in a mixer for 5 minutes using the following formulation, I would like to create a combination using an extruder.Cylinder temperature 230'C1240'C, head die temperature 250
t, rotation speed 20 rpm). After extrusion was repeated 5 times, a test piece was made using this combination using an injection molding machine (cylinder temperature 240°C, nozzle temperature 250°C,
Injection pressure 475Kg/ci).

A light resistance test was conducted using the obtained test piece 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 below.

<Blend> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 Dilauryl thiodipropionate 0.2 Stabilizer (see Table 3 below) 0.2 Table 3 Example 4 <Blend> Polyethylene 10Q Parts by weight Calcium stearate 1.0 Distearyl thiodipropionate 0.3 Stabilizer (see Table 4 below) o, 2 The above blend was kneaded and pressed to form a sheet with a thickness of 1.5 m+e. Using this sheet, the light resistance was measured in a weather oven, and the time until it became brittle was measured.

The results are shown in Table 4 below.

Table 4 Example 5 Blend> Part by weight Polyvinyl chloride (Vinyl chloride 37H) 100 Di-2-ethylhexyl phthalate 45 Barium stearate
O13 Barium nonylphenate 0.3 Zinc stearate 0.6 Octyl diphenyl phosphite 0.5 Sorbitan monopalmitate 2.0 Methylene bisstearylamide 0.3 Stabilizer (see Table 5 below) 0.1 Above combination A film having a thickness of 0.11 I+m was prepared using a kneading roll. Weather off using this film
A weather resistance test was conducted in a turret. The results are shown in Table 5 below.
Shown below.

Table 5 Example 6 <Blend> ABS resin 100 Parts by weight Stabilizer (see Table 6 below) 0.25 The above blend was kneaded with rolls and then pressed to create a sheet with a thickness of 3ffl111. Using this sheet, the residual tensile strength was measured after 800 hours of irradiation in a weather heater. The results are shown in Table 6 below.

Table 6 Example 7 Mixture> Barium stearate 0.7 Zinc stearate 0,32.6-di-tert-butyl-p-cresol 0.1 Stabilizer (see Table 7 below)
0.5 The above formulation was kneaded on a roll for 5 minutes at 70°C,
A sheet with a thickness of 0.5 mm was prepared by pressing at 0° C. for 5 minutes. 50 on a fade meter using this sheet
The residual elongation rate after time irradiation was measured. The results are shown in the table below.
7.

Table 7 Example 8 The stabilizer component (copolymer) of the present invention is also useful as a light stabilizer for paints. In this example, a two-layer metal coating consisting of a base coat containing a gold B pigment and a transparent top coat was used. We looked at the effect of glossy paint.

a) Base coat paint methyl methacrylate 100g, n-butyl acrylate 6
6g, 2-hydroxyethyl methacrylate 30g1 methacrylic acid 4g1 xylene 80g and n-butanol 2
0g, heated to 110°C while stirring, added 2g of azobisisobutyronitrile, 0.5g of dodecylmercaptan,
A solution consisting of 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,
An acrylic resin solution having a resin solid content of 50% was prepared.

12 parts by weight of the above acrylic resin solution, 2.5 parts by weight of butoxylated methylolmelamine (manufactured by Mitsui Toatsu Co., Ltd.; Kneepan 203E60; resin solid content 60%), cellulose acetate-I
・50 parts of butyrate resin (20% butyl acetate solution), 5.5 parts of aluminum pigment (manufactured by Toyo Aluminum Co., Ltd.; Alpaste 1123N), 10 parts by weight of xylene,
Butyl acetate 20 double star parts and copper fucrosoanine blue〇,
2 parts by weight was taken and used as a base coat paint.

b)) Tubucoat paint 48 parts by weight of the above acrylic resin solution, 10 parts by weight of butoxated methylolmelamine, 10 parts by weight of xylene, 1.4 parts by weight of butyl glycol acetate, and stabilizer (Table 8 below)
Reference) 0.15 parts by weight (0.5% based on solid content) was taken and used as a top coat paint.

A base coat paint was sprayed onto the primed steel plate so that the dry film thickness was 20 μm, and after being left for 10 minutes, a top coat paint was sprayed so that the dry film thickness was 30 μm. Immediately after leaving it for 15 minutes, it was baked at 140°C for 30 minutes to obtain a test piece.

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 8 below.

Table 8 Procedural amendment 1, indication of the case Japanese Patent Application No. 1983-22620 2, name of the invention Polymer material composition with improved photostability 3, person making the amendment Relationship with the case Patent applicant Adeka. Argus Chemical Co., Ltd. 4, Agent No. 601 Nogizaka, 9-6-29 Akasaka, Minato-ku, Tokyo Voluntary amendment (amendment within 1 year and 3 months from the filing date) 6. Detailed description of the invention in the specification to be amended column.

7. Contents of correction

Claims (1)

Scope of Claims: A copolymer having a molecular weight of 500 to 50,000 and having a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II) in 100 parts by weight of a polymeric material. A polymeric material composition with improved photostability, which contains .001 to 5 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a hydrogen atom, a halogen atom, or an alkyl group, R_2 represents an alkyl group or an aralkyl group, and R_3 and R_4 each represent a hydrogen atom or an alkyl group. ) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_5 is a hydrogen atom, an alkyl group, or -CO-X
_1-R_8, R_6 is -CO-X_1-R_6 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_7 is 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 may also jointly represent ▲There are mathematical formulas, chemical formulas, tables, etc.▼. X_1 and X_2 each represent -O- or -N(R_9)-, R_8 and R_9 each represent a hydrogen atom, an alkyl group, or ▲a mathematical formula, a chemical formula, a table, etc., and Z represents a ▲a mathematical formula, a chemical formula, a table, etc. etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates R_1_0
represents a hydrogen atom, oxyl, an alkyl group, or an acyl group, and R_1_1 represents an alkyl group. )