JPH0730251B2 - Polymer material composition with improved light resistance - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polymer material composition having improved light resistance, and more particularly, by adding a light stabilizer-bonded polysiloxane compound, The present invention relates to a polymer material composition having improved light resistance over a long period of time.

[Conventional technology and its problems]

Polymer materials such as polyethylene, polypropylene, styrene resin, and polyvinyl chloride deteriorate due to the action of light,
It is known that it causes discoloration or deterioration of mechanical strength and cannot withstand long-term use.

Therefore, in order to prevent deterioration of the polymer material, various light stabilizers have been conventionally used. As these light stabilizers, hindered amine-based light stabilizers and benzophenone-based or benzotriazole-based UV absorbers are mainly used, but most of these light stabilizers are low molecular weight compounds, and It has a drawback that it is volatilized during the processing of the material or when it is used at a high temperature, or it is easily extracted with water or an organic solvent, which is unsatisfactory in practice.

Therefore, it has been proposed to make the light stabilizer have a high molecular weight, and some improvement has been obtained.

For example, JP-A-52-141883 discloses a high molecular weight light stabilizer derived from a light stabilizer having two functional groups such as a polysilyl ester compound of a glycol having a polyalkylpiperidyl group. There is. However, the compounds described in this publication are limited to those derived from polyalkylpiperidine compounds having two functional groups, and other types of high molecular weight light stabilizers are not described.

Further, as a high molecular weight light stabilizer, vinyl compounds having a light stabilizer group, for example, esters of unsaturated carboxylic acids, polymers of vinyl or allyl ethers, allylamine compounds, styrenic compounds, etc. have been proposed. It is difficult to control the molecular weight of the unsaturated compound, and the polymer is obtained as a mixture having a wide molecular weight distribution. Since it necessarily contains a low molecular weight compound, the disadvantages of the low molecular weight light stabilizer described above are completely eliminated. It was difficult to do.

[Means for solving problems]

The present inventors have conducted extensive studies in order to obtain a novel type of high molecular weight photostabilizer, and as a result, the hydrogen atom of the polysiloxane compound having a repeating unit represented by the following general formula (I) is active. It is possible to easily add a vinyl or allyl compound, and by using a compound having a light stabilizer group represented by the following general formula (II) as the vinyl or allyl compound, the following general formula (III)
A high molecular weight photostabilizer having a repeating unit represented by can be easily obtained, and the photostabilizer is easy to control the molecular weight and does not contain a low molecular weight compound. It was found that the drawbacks associated with can be eliminated.

The present invention has been made based on the above findings, and based on 100 parts by weight of a polymer material, a polysiloxane compound having 5 to 50 repeating units represented by the following general formula (I) and the following general formula (II ) At least one of the compounds represented by the following general formula (II) or a mixture of at least one of the compounds represented by the following general formula (II) and other α-olefin compounds, which is represented by the following general formula in the molecule: The present invention provides a polymeric material composition having improved light resistance, which is obtained by adding 0.001 to 5 parts by weight of a polysiloxane compound having at least one repeating unit represented by (III).

[In the above formulas, R ₁ represents an alkyl group, and n is 0 or 1
And X represents a group represented by the following general formula (IV), (V) or (VI).

(R ₂ represents a hydrogen atom, an alkyl group or an acyl group,
Y is an oxygen atom or -N (R ₅₎ - indicates, R ₅ represents a hydrogen atom or an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group or a halogen atom, and Z represents a direct bond or an oxygen atom. )] Hereinafter, the polymer material composition of the present invention will be described in detail.

In each of the above formulas, the alkyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, Amyl, tertiary amyl, octyl, tertiary octyl, etc., and the acyl group represented by R ₂ includes, for example, formyl, acetyl, propionyl, butyroyl, benzoyl, etc., and is represented by R ₃ and R ₄ . Examples of the halogen atom include a chlorine atom, a bromine atom and a fluorine atom.

The polysiloxane compound having the repeating unit represented by the general formula (I) is a known compound, and compounds having various degrees of polymerization are commercially available and can be used as they are.

Further, the compound represented by the general formula (II), which is a vinyl or allyl compound having any one of the groups represented by the general formula (IV), (V) or (VI), is a known compound, and a typical example thereof is shown. As, for example, 2,2,6,6-tetramethyl-4
-Aryloxypiperidine, 1,2,2,6,6-pentamethyl-
4-Aryloxypiperidine, 2,2,6,6-tetramethyl-
Vinyloxypiperidine, 1,2,2,6,6-pentamethyl-4
-Vinyloxypiperidine, 1-acetyl-2,2,6,6-tetramethyl-4-allyloxypiperidine, 2,2,6,6-tetramethyl-4- (N-butyl-N-allylamino) piperidine, 1,2,2,6,6-pentamethyl-4- (N-methyl-N-allylamino) piperidine, 2-hydroxy-
4-vinyloxybenzophenone, 2-hydroxy-4-
Allyloxybenzophenone, 2- (2-hydroxy-3
-Allyl-5-methylphenyl) benzotriazole,
2- (2-hydroxy-5-vinylphenyl) benzotriazole, 2- (2-hydroxy-3-allyl-5)
Tertiary octylphenyl) benzotriazole, 2- (2
-Hydroxy-3-allyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
4-allyloxyphenyl) benzotriazole and the like can be mentioned.

Further, as the other α-olefin compound which can be used together with the compound represented by the general formula (II), if necessary, ethylene, propylene, butene, octene,
Examples include decene, dodecene, tetradecene, hexadecene, octadecene, vinyl methyl ether, vinyl butyl ether, allyl butyl ether, trifluoropropylene and the like.

The compound having a repeating unit represented by the general formula (III), which is used as a stabilizer in the present invention, includes a polysiloxane compound having a repeating unit represented by the general formula (I) and a compound represented by the general formula (II). A compound represented by (and other α-olefin compound as necessary),
In the presence of chloroplatinic acid or a siloxane-based catalyst, if necessary, it can be easily synthesized by reacting in a solvent inert to the reaction such as isopropanol, secondary butanol, tetrahydrofuran, or in the absence of a solvent. .

The reaction can be carried out in the range of room temperature to about 200 ° C, preferably about 30 ° C to about 100 ° C.

Next, specific synthesis examples of the compound having the repeating unit represented by the general formula (III) used in the present invention will be given, but the present invention is not limited by the following synthesis examples.

Synthesis Example-1 Polymethylsiloxane / 1,2,2,6,6-pentamethyl-4-
Synthesis of vinyloxypiperidine adduct (stabilizer No.1) 1 g of 1,2,2,6,6-pentamethyl-4-polymethylsiloxane (DC1107 manufactured by Dow Corning) having a degree of polymerization of about 30 (molecular weight of about 1800) 3 g of vinyloxypiperidine was dissolved in 20 ml of isopropanol, and 50 mg of chloroplatinic acid was added. 50-60
After stirring at ° C for 1 hour, isopropanol was distilled off.
Toluene was added, washed with water, dried and treated with activated carbon.

Preparative liquid chromatography fractionation, average molecular weight 45
A light gray yellow viscous liquid product of 00 was obtained.

As a result of infrared spectroscopic analysis, this product was found to be 2850, 1370, 138
There is absorption at 0,1020 to 1160 cm ^-1 , and the nitrogen content of the product is 4.2%, so about 44% of Si-H has 1,2,
It was confirmed to be a product (target product) to which 2,6,6-pentamethyl-4-vinyloxypiperidine was added.

Synthesis Example-2 Polymethylsiloxane / 1,2,2,6,6-pentamethyl-4-
Synthesis of vinyloxypiperidine adduct (stabilizer No.2) Polymethylsiloxane 1 with degree of polymerization of about 30 (molecular weight of about 1800)
2.8 g, 1,2,2,6,6-pentamethyl-4-vinyloxypiperidine 50 g and Down Corning siloxane catalyst 150
After taking mg, the mixture was stirred at 60 to 70 ° C for 6 hours.

Add xylene, wash with water, dry and treat with 1% activated carbon,
After filtration, desolvation was performed to obtain a pale grayish yellow viscous liquid product having an average molecular weight of about 7,000.

As a result of infrared spectroscopic analysis, this product was found to be 2850, 1370, 138
There is absorption at 0,1020 to 1160 cm ^-1 , and the nitrogen content of the product is 5.3%, so about 90% of Si-H has 1,2,
It was confirmed to be a product (target product) to which 2,6,6-pentamethyl-4-vinyloxypiperidine was added.

Synthesis Example-3 Polymethylsiloxane / 1,2,2,6,6-pentamethyl-4-
Synthesis of allyloxypiperidine adduct (stabilizer No.3) Polymethylsiloxane 32 with degree of polymerization of about 10 (molecular weight of about 600) 32
g, 1,2,2,6,6-pentamethyl-4-aryloxypiperidine 116 g and Dow Corning siloxane catalyst 360 mg were taken and stirred at 60 to 70 ° C. for 6 hours.

Add xylene, wash with water, dry and treat with 1% activated carbon,
After filtration, the solvent was removed to obtain a pale grayish yellow viscous liquid product having an average molecular weight of about 2600.

As a result of infrared spectroscopic analysis, this product was found to be 2850, 1370, 138
There is absorption at 0,1030 to 1140 cm ^-1 , and the nitrogen content of the product is 5.1%, so about 90% of Si-H has 1,2,
It was confirmed that the product (target product) was obtained by adding 2,6,6-pentamethyl-4-allyloxypiperidine.

Synthesis Example-4 Polymethylsiloxane / 1,2,2,6,6-pentamethyl-4-
Synthesis of allyloxypiperidine adduct (stabilizer No.4) Polymethylsiloxane 1g with degree of polymerization of about 30 (molecular weight of about 1800)
And 1,2,2,6,6-pentamethyl-4-allyloxypiperidine 3 g was dissolved in 20 ml of isopropanol and chloroplatinic acid was added.
50 mg was added. After stirring at 50-60 ° C for 1 hour, isopropanol was distilled off. Toluene was added, washed with water, dried and treated with activated carbon.

Preparative liquid chromatography, molecular weight about 4500
The product was obtained as a pale grayish yellow viscous liquid.

As a result of infrared spectroscopic analysis, this product was found to be 2850, 1370, 138
There is absorption at ⁰ , 1030 to 1140 cm ^-1 and the nitrogen content of the product is 4.0%, so about 43% of Si-H is 1, 2,
It was confirmed that the product (target product) was obtained by adding 2,6,6-pentamethyl-4-allyloxypiperidine.

Synthesis Example-5 Polymethylsiloxane / 1,2,2,6,6-pentamethyl-4-
Aryloxypiperidine / dodecene co-adduct (Stabilizer No.
Synthesis of 5) Polymethylsiloxane with a degree of polymerization of about 30 (molecular weight of about 1800) 1.
3 g and 1.3 g of 1,2,2,6,6-pentamethyl-4-allyloxypiperidine were dissolved in 20 ml of isopropanol and 50 mg of chloroplatinic acid was added. After stirring at 60 ° C. for 15 minutes, a portion of this was taken and treated in the same manner as in Synthesis Example-3. As a result, about 22% of Si—H was converted to 1,2,2,6,6-pentamethyl-4-vinyloxy. A reaction product to which piperidine was added was obtained.

After confirming that the absorption based on Si—H at 2250 cm ⁻¹ remained by infrared spectroscopy, 1-dodecene was added to the reaction product.
1 g was added, and the mixture was stirred at 60 ° C for 30 minutes. After distilling off isopropanol, it was extracted with toluene. The product was washed with water, dried, treated with sodium borohydride, washed again with water and then desolvated to obtain a pale ash yellow viscous liquid product having a molecular weight of about 3700.

As a result of infrared spectroscopic analysis, this product was found to be 2850, 1370, 138
It was confirmed that the product was the target since there was absorption at 0,1020 to 1160 cm ^-1 and the nitrogen content of the product was 2.5%.

Synthesis Example-6 Polymethylsiloxane / 2,2,6,6-tetramethyl-4-
Synthesis of (N-butyl-N-allylamino) piperidine adduct (stabilizer No.6) Polymethylsiloxane 1g with degree of polymerization of about 18 (molecular weight of about 1100)
And 2,2,6,6-tetramethyl-4- (N-butyl-N-
1 g of allylamino) piperidine was dissolved in 15 ml of isopropanol, and 70 mg of chloroplatinic acid was added. After stirring at 60-80 ℃ for 5 hours, distilling off isopropanol, adding benzene, washing with water, drying and removing the solvent, the molecular weight was about 3400.
The product was obtained as a pale grayish yellow viscous liquid.

As a result of infrared spectroscopic analysis, this product was 3300, 1370 to 138.
There is absorption at ⁰ , 1020 to 1050 cm ^-1 , and the nitrogen content of the product is 7.5%, so about 51% of Si-H has 2,2,
It was confirmed to be a product (target product) to which 6,6-tetramethyl-4- (N-butyl-N-allylamino) piperidine was added.

Synthesis Example-7 Synthesis of polymethylsiloxane / 2-hydroxy-4-allyloxybenzophenone adduct (stabilizer No. 7) Polymethylsiloxane having a polymerization degree of about 18 (molecular weight of about 1100).
3 g and 2-hydroxy-4-allyloxybenzophenone
Dissolve 0.3 g in 10 ml of isopropanol and add chloroplatinic acid 15
mg was added. The mixture was stirred at 40 to 50 ° C. for 1 hour, isopropanol was distilled off, hexane was added, the mixture was washed with water, dried and then desolvated to obtain a pale ash yellow viscous liquid product having a molecular weight of about 3500.

As a result of infrared spectroscopic analysis, this product was found to be 1640, 1020-1160.
There is absorption at cm ^-1 , and about 52% of Si-H is 2-hydroxy-
It was confirmed to be a product (target product) to which 4-allyloxybenzophenone was added.

Synthesis Example-8 Synthesis of polymethylsiloxane / 2 (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole adduct (stabilizer No.8) 1 g of polymethylsiloxane having a degree of polymerization of about 30 (molecular weight of about 1800)
And 2- (2-hydroxy-3-allyl-5-methylphenyl) benzotriazole (3 g) were dissolved in 20 ml of isopropanol, and 50 mg of chloroplatinic acid was added. After stirring at 50-60 ° C for 1 hour to distill off isopropanol, add toluene and wash with water, dry and remove the solvent to remove the solvent.
A light gray yellow viscous liquid product of 00 was obtained.

As a result of infrared spectroscopic analysis, this product has absorption at 1540 and 750 cm ⁻¹ , and since the nitrogen content of the product is 6.3%, it is 2- (2) about 15% of Si—H. -Hydroxy-3
It was confirmed that the product (target product) was obtained by adding -allyl-5-methylphenyl) benzotriazole.

The present invention is to use the polysiloxane compound having a specific light stabilizer group as a stabilizer for a polymer material, the addition amount is usually 0.0 to 100 parts by weight of the polymer material.
The amount is 01 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

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, ethylene-propylene copolymers. Polyolefins such as coalesce and copolymers thereof, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyfluorinated vinylden, 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,
Copolymers of polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene with other monomers (eg maleic anhydride, N-phenylmaleimide, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene. Copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, methacrylate resin such as polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyphenylene oxide, Polyamide, polycarbonate, polyacetal, polyurethane, fibrous resin, or phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin It can be mentioned. 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.

In the composition of the present invention, the polysiloxane compound having the repeating unit represented by the general formula (III) can be used in combination with other general-purpose additives such as antioxidants and stabilizers.

Particularly preferable as these other additives are:
Antioxidants such as phenol type, sulfur type, phosphite type,
Other light stabilizers may be mentioned.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol and 2,6-diphenyl-4.
-Octoxyphenol, stearyl- (3,5-di-methyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl- 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
2,4,6-Tris (3 ', 5'-di-tert-butyl-4-hydroxybenzylthio) 1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl) ) Benzylmalonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-) m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-second)
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-third
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-actylthio-4,6-di (4-hydroxy-3,5-di-tertiary
Butyl) phenoxy-1,3,5-triazine, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol)
Monoacrylate, triethylene glycol bis [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis (1,1-dimethyl-2)
-Hydroxyethyl) 2,4,8,10-tetraoxaspiro [5,5] undecane bis [3- (3-tert-butyl-4-
Hydroxy-5-methylphenyl) propionate] and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl-. (For example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) esters (for example, pentaerythritol tetralauryl thiopropionate) can be mentioned.

Further, as the phosphite-based antioxidant, for example,
Trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl)
Phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5) - tert-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ ~ ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3 -Methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono / di mixed nonylphenyl) phosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, bis (octylphenyl) -bis [4,4'-bu Chilidenbis (3-
Methyl-6-tert-butylphenol), 1,6-hexanediol diphosphite phenyl, 4,4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-tert-butylphenol) pentaerythritol Diphosphite, bis (2,6-di-third
Butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidene bis (2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl)
Pentaerythritol diphosphite, tris (1,3-
Di-stearoyloxyisopropyl) phosphite,
4,4'-isopropylidene bis (2-tert-butylphenol) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis ( 2,4-di-tertiary butylphenyl) -4,4'-biphenylenediphosnite and the like can be mentioned.

Examples of the other light stabilizers described above include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2 Hydroxybenzophenones such as 4,4-dihydroxybenzophenone, 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'-di-t-amylphenyl) benzotriazole and other benzotriazoles, phenyl salicylate, pt-butylphenyl Benzoates such as salicylate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2 '-Thiobis (4-t-octylphenol) Ni salt, [2,2'-thiobis (4-t
-Octylphenolate)]-n-butylamine Ni,
Nickel compounds such as (3,5-di-t-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, α-cyano-β-methyl-β- (p-methoxyphenyl) acryls methyl, etc. Substituted acrylonitriles and N-2-ethylphenyl-N'-2-ethoxy-5-
Examples thereof include oxalic acid dianilides such as tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide.

In the composition of the present invention, if necessary, other heavy metal deactivators, nucleating agents, metal soaps, organotin compounds, plasticizers,
Epoxy compound, pigment, filler, foaming agent, antistatic agent,
Flame retardants, lubricants, processing aids, etc. can be added.

The polymeric material composition of the present invention can be used in a wide variety of forms, for example, as films, fibers, tapes, sheets, various molded products, and also as paints, binders for lacquers, adhesives,
It can be used as a base material in putty and photographic materials.

Next, the present invention will be specifically described with reference to examples.

However, the invention is not limited to these examples.

Example 1 <Distribution> Polypropylene 100 parts by weight Tetrakis [methylene-3 (3,5-ditertiary butyl-4-]
Hydroxyphenyl) propionate] methane 0.1
Calcium stearate 0.05 Stabilizer (see Table-1) 0.2 A press sheet having a thickness of 0.3 mm was prepared with the above composition, and a light resistance test was performed on this sheet 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 24 hours. The results are shown in Table 1 below.

* 1: Comparative compound A Poly (1,2,2,6,6-pentamethyl-4-vinyloxypiperidine) Molecular weight: 5,600 * 2: Comparative compound B Dimethyldichlorosilane / 1- (2-hydroxyethyl)
-2,2,6,6-Tetramethyl-4-hydroxypiperidine polycondensate Molecular weight: 1,400 * 2: Comparative compound C 1,2,2,6,6-pentamethyl-4-vinyloxypiperidine Example 2 Normal It is known that the stabilizer loses its effect remarkably due to volatilization, decomposition and the like during high temperature processing of the resin.

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 repeating the extrusion 10 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 tests were carried out for one and five extrusions. The results are shown in Table 2 below.

<Blend> 100 parts by weight of ethylene-propylene copolymer resin Calcium stearate 0.2 Stearyl-β-3,5-di-tert-butyl-4-hydroxyphenylpropionate 0.1 Dilaurylthiodipropionate 0.3 Stabilizer (Table-2 Refer) 0.2 Example 3 <Compounding> Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3- (3,5-ditertiary butyl-4]
-Hydroxyphenyl) propionate] methane 0.1
Distearyl thioazipropionate 0.3 Stabilizer (see Table 3) 0.2 The above composition 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 3 below.

Example 4 <Formulation> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Trisnonylphenyl phosphite 0.2 Ca-stearate 0.1 Zn-stearate 0.1 Stabilizer (see Table 4) 0.2 Roll the above formulation The above was kneaded to form a sheet having a thickness of 1 mm. Using this sheet, a light resistance test in a weatherometer was conducted. The results are shown in Table 4 below.

Example 5 <Compounding> Polyurethane resin (U-100 manufactured by Asahi Denka Co., Ltd.) 100 parts by weight Ba-stearate 0.7 Zn-stearate 0.3 2,6-tert-butyl-p-cresol 0.1 Stabilizer (see Table-5) 0.3 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 and 100 hours was measured with a fade meter. The results are shown in Table-5 below.
Shown in.

Example 6 The compounds of the present invention are also useful as light stabilizers for coatings. In this example, the effect was observed with 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 methacrylmethyl, 66 g of n-butyl acrylate, 30 g of 2-hydroxyethyl methacrylate, 4 g of methacrylic acid
g, 80 g of xylene and 20 g of n-butanol were taken and a solution consisting of 2 g of azobisisobutyronitrile, 0.5 g of dodecyl mercaptan, 80 g of xylene and 20 g of n-butanol was added dropwise over 3 hours while stirring at 110 ° C. 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, butoxylated methylol melamine (manufactured by Mitsui Toatsu Co., Ltd .; Uban 20SE60; resin solid content 6)
0%) 2.5 parts by weight, cellulose acetate butyrate resin (20% butyl acetate solution) 50 parts by weight, aluminum pigment (Toyo Aluminum Co .; Alpaste 1123N) 5.5 parts by weight, xylene 10 parts by weight, butyl acetate 20 parts by weight and 0.2 parts by weight of copper phthalocyanine blue was taken as a base coat paint.

b) Top coat 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 0.12 parts by weight of a stabilizer (see Table 6) (0.4 based on solid content). %) To obtain a top coat paint.

The base coat paint was sprayed on the primer-treated steel sheet 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 μm. 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 6 below.

[Effect of the Invention] The polymer material composition of the present invention is excellent in stability, particularly in light resistance, for a long period of time.

Claims (1)

[Claims] 1. A polysiloxane compound having 5 to 50 repeating units represented by the following general formula (I) per 100 parts by weight of a polymer material, and at least a compound represented by the following general formula (II). One, or an addition reaction product with at least one compound represented by the following general formula (II) and a mixture of other α-olefin compounds, which is a repeating unit represented by the following general formula (III) in the molecule. A polymeric material composition having improved light resistance, which is obtained by adding 0.001 to 5 parts by weight of a polysiloxane compound having at least one unit. [In the above formulas, R ₁ represents an alkyl group, and n is 0 or 1
And X represents a group represented by the following general formula (IV), (V) or (VI). (R ₂ represents a hydrogen atom, an alkyl group or an acyl group,
Y is an oxygen atom or -N (R ₅₎ - indicates, R ₅ represents a hydrogen atom or an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group or a halogen atom, and Z represents a direct bond or an oxygen atom. )]