JPH0196259A - High polymer material composition having improved light resistance - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved light resistance, causing neither change of color nor reduction in mechanical strength, by blending a high polymer material with a siloxane composition bonded to a specific light stabilizer. CONSTITUTION:100pts.wt. high polymer material such as polyethylene is blended with (A) a polysiloxane compound having 5-50 repeating units shown by formula I (R1 is alkyl) and (B) 0.001-5pts.wt. polysiloxane compound which is (i) a compound shown by formula II {X is group shown by formula III, IV or V [R2 is H, alkyl or acyl; Y is oxygen atom., -N(R5)- (R5 is H or alkyl); R3 and R4 are H, alkyl or halogen; Z is direct bond valence or oxygen atom.]} or (ii) an adduct of a compound shown by formula II with another alpha-olefin compound and has one repeating unit shown by formula VI to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a polymeric material composition with improved light resistance, and more particularly, by adding a polysiloxane compound to which a light stabilizer is attached. The present invention relates to a polymeric material composition with 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 a decrease in mechanical strength, and cannot withstand long-term use.

Therefore, in order to prevent the deterioration of polymeric materials, various light stabilizers have been conventionally used. As these light stabilizers, hindered amine light stabilizers, hensifenone-based or benzotriazole-based ultraviolet absorbers are mainly used, but most of these light stabilizers are low molecular weight compounds, and polymers It has the disadvantage that it volatilizes during material processing or when used at high temperatures, or is easily extracted by water or organic solvents, and is unsatisfactory in practice.

For this reason, it has been proposed to increase the molecular weight of the light stabilizer, and some improvement has been achieved.

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 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.

In addition, as high molecular weight light stabilizers, vinyl compounds having light stabilizer groups, such as esters of unsaturated carboxylic acids, vinyl or allyl ethers, allylamine compounds, and polymers such as styrene compounds have also been proposed. It is difficult to control the molecular weight of unsaturated compound polymers, and they are obtained as a mixture with a wide molecular weight distribution, and they inevitably contain low molecular weight compounds, completely eliminating the disadvantages of the low molecular weight light stabilizers mentioned above. It was difficult to do so.

[Means for solving problems]

As a result of repeated studies to obtain a new type of high-molecular-weight photostabilizer, the present inventors discovered that the following - maximum (I)
The hydrogen atom of the polysiloxane compound having the repeating unit represented by is active, and it is possible to easily add a vinyl or allyl compound. By using compounds with stabilizer groups, the following - maximum (
It is possible to easily obtain a high-molecular-weight light stabilizer having a repeating unit represented by [[ It has been discovered that the drawbacks associated with molecular weight light stabilizers can be overcome.

The present invention was made based on the above findings, and includes a polysiloxane compound having 5 to 50 repeating units represented by the following maximum (I), and a polysiloxane compound having 5 to 50 repeating units represented by the following maximum An addition reaction product with at least one compound represented by I, or a mixture of at least one compound represented by (II) below and other α-olefin compounds, which has the following in the molecule: max(I[[)
0.001 to 5 parts by weight of a polysiloxane compound having at least one repeating unit represented by:
The present invention provides a polymeric material composition with improved light resistance.

R2 ■-3i-0-(I) CHz=CIl(CHz
), lX (II)■ +1 R+ -3i-0-(m) GHzGHz (C1l□). X [In each of the above formulas, R8 represents an alkyl group, n represents 0 or l, and X represents the following formula (IV), (V) or (V
Indicates any group of l).

(R1 represents a hydrogen atom, an alkyl group, or an acyl group, Y represents an oxygen atom or -N(I15)-, and R2 represents a hydrogen atom or an alkyl group. R3 and R9 each represent a hydrogen atom, an alkyl group, or an acyl group. represents a halogen atom, and Z represents a direct bond or an oxygen atom)] The polymer material composition of the present invention will be described in detail below.

In each of the above formulas, examples of the alkyl group represented by R+, Rz, R3, R4 and R5 include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tert-butyl, isobutyl, amyl, tertiary amyl, Examples of the acyl group represented by Rz include formyl, acetyl, propionyl, butyroyl, benzoyl, etc., and halogen atoms represented by R1 and R6 include, for example, Examples include chlorine atom, bromine atom, and fluorine atom.

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

Further, the compound represented by the above-mentioned tubular formula (II), which is a vinyl or allyl compound having any group of the above-mentioned tubular formula (IV), (V) or (Vl), is a known compound; Representative examples include, for example, 2.2,6.6-tetramethyl-4-allyloxypiperidine, 1.2,2,6
．． 6-bentamethyl-4-allyloxypiperidine, 2,
2.6.6-Tetramethyl-4-vinyloxypiperidine, ■.

2.2,6. G-pentamethyl-4-vinyloxypiperidine, 1-acetyl-2,2,6,6-tetramethyl-
4-allyloxypiperidine, 2,2゜6.6-titramethyl-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
-Aryloxybenzophenone, 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)-5-10 lobenzotriazole, 2-(2-hydroxy-4-allyloxyphenyl)benzotriazole, and the like.

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

The above-mentioned tube type (
A compound having a repeating unit represented by I[
and other α-olefin compounds as necessary) in the presence of a chloroplatinic acid or siloxane catalyst, and as necessary a solvent inert to the reaction such as isopropanol, sec-butanol, tetrahydrofuran, etc. It can be easily synthesized by reacting in a vacuum or without a solvent.

The reaction may be carried out at a temperature ranging from room temperature to about 200<0>C, but preferably from about 0<0>C to about 100<0>C.

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

Synthesis Example-1 1 g of polymethylsiloxane (DCIIO7 manufactured by Dow Corning) with a degree of polymerization of about 30 (molecular weight 1800) and 1.
2.2.6.3 g of 6-bentamethyl-4-vinyloxypiperidine was dissolved in 20 ml of isopropanol and 50 ml of chloroplatinic acid was added. After stirring at 50 to 60°C for 1 hour, isopropanol was distilled off. Toluene was added, washed with water, dried, and treated with activated carbon.

The product was separated by preparative liquid chromatography to obtain a fly ash yellow viscous liquid product with an average molecular weight of 4,500.

As a result of infrared spectroscopy, this product was found to be 285o, 137
There is absorption at 0.1380.1020 to 1160 cm-', and since the nitrogen content of the product is 4.2%, about 44% of 5i-H has an absorption of 1,2°2.6.6-'. Product with addition of bentamethyl-4-vinyloxypiperidine (
It was confirmed that it was the target object.

Synthesis Example-2 12.8 g of polymethylsiloxane with a degree of polymerization of about 30 (molecular m about 1800), 50 g of 1,2,2,6.6-bentamethyl-4-vinyloxypiperidine, and 150 cm of siloxane catalyst manufactured by Dow Corning were taken. , and stirred at 60-70°C for 6 hours IS'2.

Add xylene, wash with water, dry, and then treat with 1% activated carbon.
After filtration, the product was washed with m solvent to obtain a fly ash yellow viscous liquid product with an average molecular weight of 7,000.

As a result of infrared spectroscopy, this product was found to be 2850.137
There is absorption at 0.1380.1020 to 1160 cm-', and since the nitrogen content of the product is 5.3%, about 90% of 5i-H has an absorption of 1.2°2.6. It was confirmed that the product was an addition product (target product) of 6-bentamethyl-4-vinyloxypiperidine.

Synthesis Example-3 Take 32 g of polymethylsiloxane with a degree of polymerization of about 10 (molecular weight 600), 116 g of 1,2,2.6.6-bentamethyl-4-oxypiperidine, and 360 nv of siloxane catalyst manufactured by Dow Corning Co., Ltd. Stirred at ~70°C for 6 hours.

Add xylene, wash with water, dry, and then treat with 1% activated carbon.
After filtration, the solvent was removed to obtain a fly ash yellow viscous liquid product with an average molecular weight of 2,600.

As a result of infrared spectroscopy, this product was found to be 2850.137
There is absorption at 0.1380.1030 to 1140 cm-', and since the nitrogen content of the product is 5.1%, about 90% of 5i-H has an absorption of 1.2°2.6.6-'. Product with addition of bentamethyl-4-allyloxypiperidine (
It was confirmed that it was the target object.

Synthesis Example-4 1 g and 1,2,2,6.6-bentamethyl-4- polymethylsiloxane with a degree of polymerization of about 30 (molecular weight 1800)
3 g of allyloxypiperidine was dissolved in 20 ml of isopropanol, and 50 ml of chloroplatinic acid was added. After ffl stirring at 50 to 60°C for 1 hour, isopropanol was distilled off.

Toluene was added, washed with water, dried, and treated with activated carbon.

Separated by preparative liquid chromatography, molecular weight approximately 45
A product of 0.00 fly ash yellow viscous liquid was obtained.

As a result of infrared spectroscopy, this product was found to be 2850, l37
There is an absorption at 0.1380.1030~l l 40 cm-', and since the nitrogen content of the product is 4.0%, about 43% of 5i-H has an absorption of 1.2°2.6. It was confirmed that the product was an addition product (target product) of G-pentamethyl-4-allyloxypiperidine.

Synthesis Example-5 1.3 g of polymethylsiloxane with a degree of polymerization of about 30 (molecular weight 1800) and 1. 2. 2. 6. 1.3 g of 6-bentamethyl-4-allyloxypiperidine was dissolved in 202 isopropanol, and 20 m+r 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. Approximately 2
A reaction product was obtained in which 1.2,2.6°6-bentamethyl-4-vinyloxypiperidine was added to 2%.

After confirming that SiH-based absorption at 2250cn+-' remained by infrared spectroscopy, 1g of 1-dodecene was added to the reaction product, and the mixture was stirred at 60°C for 30 minutes.
I did it. After distilling off the isopropanol, the mixture was extracted with toluene. After washing with water and drying, it is treated with sodium borohydride, and after washing with water again, the molecular placement piece 37 is treated with a solvent.
A product of 0.00 fly ash yellow viscous liquid was obtained.

As a result of infrared spectroscopy, this product was found to be 2850.137
Since there was absorption at 0.1380.1020 to 1160 cm-' and the nitrogen content of the product was 2.5%, it was confirmed that it was the desired product.

Synthesis Example-6 Polyethylene with a degree of copolymerization of about 18 (molecular weight about 1100) containing piperidine-4 and 2,2,6.6-titramethyl-4 -(N
-butyl-N-allylamino)piperidine 1g to 15-
The mixture was dissolved in isopropanol and 70 μl of chloroplatinic acid was added. After stirring at 60 to 80°C for 5 hours and distilling off isopropanol, benzene was added, washing with water, drying, and removing the solvent gave a fly ash yellow viscous liquid product with a molecular weight of 3400.

As a result of infrared spectroscopy, this product was found to be 3300.137
There is an absorption at 0 to 1380.1020 to I O50 cm-', and since the nitrogen content of the product is 7.5%, about 51% of Si-H contains 2,2°6.6-titramethyl- It was confirmed that the product was an addition product (target product) of 4-(N-butyl-N-allylamino)piperidine.

Synthesis Example-7 Polymethylsiloxane/2-Hydroxy-4-allyloxyhensiphenone 0.3 g of polymethylsiloxane with a degree of dish polymerization of about 18 (molecule number 1100) and 2-hydroxy 0.3 g of -4-allyloxybenzophenone was dissolved in 10-isopropanol and 15 ml of chloroplatinic acid was added. 1 at 40-50°C
After stirring for a period of time and distilling off isopropanol, hexane was added, washing with water, drying, and solvent removal to obtain a fly ash yellow viscous liquid product with a molecular weight of 3500.

As a result of infrared spectroscopy, this product was found to be 1640, L O
2 (I to L 160 cm-'), and it was confirmed that the product was a product (target product) in which 2-hydroxy-4-allyloxybenzophenone was added to about 52% of 5i-H.

Synthesis Example-8 1 g of polymethylsiloxane with a degree of polymerization of about 30 (molecular weight 1800) and 2-(2-hydroxy-3-allyl-5-
Dissolve 3 g of (methylphenyl)benzotriazole in 20-g of isopropanol.

50 ffg of chloroplatinic acid was added. After stirring at 50 to 60°C for 1 hour and distilling off isopropanol, toluene was added, washing with water, drying, and removing the solvent resulted in a molecular weight of about 30.
A product of 0.00 fly ash yellow viscous liquid was obtained.

As a result of infrared spectroscopy, this product was found to be 1540.750
There is an absorption at cm-', and the nitrogen content of the product is 6.
．． 3%, approximately 15% of 5i-TI contains 2-(
It was confirmed that the product was an addition product (target product) of 2-hydroxy-3-(5-methylphenyl)benzotriazole.

In the present invention, the polysiloxane compound having the above-mentioned specific light stabilizer group is used as a stabilizer for polymer materials, and the amount added is usually 0.001 to 5 parts by weight per 100 parts by weight of the polymer material. Part by weight, preferably 0.01 to 3 parts by weight.

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, polyvinyldene 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, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, chlorinated Vinyl-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleic ester copolymer, vinyl chloride-methacrylic ester copolymer, vinyl chloride-acrylonitrile copolymer, internal Halogen-containing synthetic resins such as plasticized polyvinyl chloride, petroleum resins, coumaron resins,
Polystyrene, polyvinyl acetate, acrylic resin, copolymers of styrene and/or α-methylstyrene with other monomers (e.g. maleic anhydride, N-phenylmaleimide, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene Copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene co-IR polymers, methacrylate resins such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyesters, polyphenylene oxide, Examples include polyamide, polycarbonate, polyacecool, polyurethane, cellulose resin, phenol resin, urea resin, melamine resin, polyamide resin, unsaturated polyester resin, and silicone resin. Furthermore,
Isoprene rubber, butadiene rubber, acrylonitrile
Rubbers such as butadiene copolymer rubber and styrene-butadiene copolymer rubber, or blends of these resins may also be used. Also included are crosslinked polymers, such as crosslinked polyethylene, whose crosslinking has been made uniform by peroxides or radiation, and foamed polymers, such as foamed polystyrene, which have been foamed with a foaming agent.

In the composition of the present invention, other general-purpose additives such as antioxidants and stabilizers can also be used together with the polysiloxane compound having a repeating unit represented by the above-mentioned -tubular formula (I[I). .

Particularly preferable examples of these other additives include:
Antioxidants such as phenol, sulfur, and phosphite,
Other light stabilizers may be mentioned.

As the above-mentioned 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-butylphenyl)propionate, distearyl-
3,5” m3butyl-4-hydroxybenzylphosphonate, 2,4.6-)lith (3°, 5゛-di 3rd
butyl-4-hydroxybenzylthio)1゜3.5. −
) riazine, distearyl(4-hydroxy-3-methyl-5-tert-butyl)penzylmalone-1, 2,2゛-methylenebis(4-methyl-6-tert-butylphenol), 4,4°-methylenebis (2,6-di-tert-butylphenol), 2,2°-methylenebis(6-(I-
methylcyclohexyl)p-cresol], bis[3゜5-bis(4-hydroxy-3-tert-butylphenyl)
Butyric acid coglycol ester, 4.4”-butylidene bis(6-tert-butyl-m-cresol), 2
．． 2″-ethylidenebis(4°6-di-tert-butylphenol), 2,2″-ethylidenebis(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) phenylcoterefucrate, 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-) Listylbenzene, Tetrakis[methylene-3-(3°5-di-tert-butyl-4-hydroxyphenyl)propio]methane, 1,3.5-1-Lis(3, 5-di-tert-butyl-4-hydroxybenzyl)
Isocyanurate, 1.3.5-)lis((3,'5-
di-tert-butyl-4-hydro;triphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-hydroxy-3,5-di-tert.
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 (I,
1-dimethyl-2-hydroxyethyl)2,4,8.1
0~Tetraoxaspiro(5,5) undecambis(3
-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like.

The sulfur-based antioxidants include, for example, dialkylthiodipropionates such as dilauryl, similystyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl. (eg glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (eg pentaerythritol tetralauryl thiopropionate).

In addition, examples of the phosphite-based antioxidants 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, distearylpentaerys, litol diphosphite, tetra(tridecyl)-1,1゜3-
Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(C+□~
, 5 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-di mixed 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-butyl phenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Tris[4,4°-isopropylidene bis(2-tert-butylphenol)]phosphite, phenyl diisodecyl phosphite, di(nonylphenyl)pentaerythritol diphosphite, tris(I,3-di-stearoyloxyisopropyl) ) Phosphite, 4.4°-
Isopropylidene bis(2-tert-butylphenol)・
Di(nonylphenyl)phosphite, 9.10-di-hydro-9-oxa-10-phosphonophenanthrene-10-oxide, tetrakis(2゜4-di-tert-butylphenyl)-4,4'-biphenylene Examples include range phosphonite.

In addition, examples of the above-mentioned other light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-
Hydroxybenzophenones such as hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3'-t-butyl-5
"-methylphenyl)-5-chlorobenzo) IJ asole, 2-(2'-hydroxy-3゛, 5°-di-t
-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-5'-methylphenyl)penztriazole, 2-(2'-hydroxy-3° 5'
-benzotriazoles such as -di-t-amylphenyl)benzotriazole, phenylsalicyle), p-L-
butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-
Benzoates such as 4-hydroxybenzoate, 2.
2′-thiobis(4-t-octylphenol) Ni salt, [2,2″-thiobis(4-t-octylphenolate))-'n-butylamine Ni, (3,5-di-
Nickel compounds such as t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, FtA acrylonitriles such as methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylics, and N-2 −
Ethylphenyl-N'-2-ethoxy-5-tert-butylphenyloxalic acid diamide, N-2-ethylphenyl-
Examples include oxalic acid dianilides such as N'-2-ethoxyphenyl oxalic acid diamide.

In addition, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, a TG compound, a plasticizer, an epoxy compound, a pigment, a filler, a blowing agent, and an antistatic agent, as necessary. additives, flame retardants, lubricants, processing aids, etc. can be added.

The polymer materials 3, 11 compositions of the present invention can be used in a wide variety of forms, such as films, fibers, tapes, sheets, various molded products, and can also be used as paints, binders for lacquers, adhesives, putties, etc. It can also be used as a base material in photographic materials.

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 Ropionate Calcium methane stearate 0.05 Stabilizer (Table 1
Reference) 0.2 A press sheet with a thickness of 0.31 was prepared using the above formulation, and a light resistance test was conducted on this sheet using a high-pressure mercury lamp. In addition, 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.
Shown below.

Table 1 Note: In Table 1 above, comparative compounds A, B and C are as follows (the same applies to Tables 2 to 6 below).

$1 = Comparative compound A Poly (I,2,2,6,6-bentamethyl-4-vinyloxypiperidine) Molecular weight: 5,600 Book 2: Comparative compound B Dimethyldichlorosilane/1-(2-hydroxyethyl)-2 , 2,6,6-tetramethyl-4-hydroxypiperidine polycondensate Molecular weight: t, 4o.

*2: Comparative Compound C 1,2,2,6,6-bentamethyl-4-vinyloxypiperidine Example 2 It is known that ordinary stabilizers lose their effectiveness significantly due to volatilization, decomposition, etc. during high-temperature processing of resins. ing.

In this example, the effects of high-temperature processing were confirmed by repeating the extrusion process.

After mixing the resin and additives in a mixer for 5 minutes according to the following formulation, a combination was created using an extruder (cylinder temperature 230°C, 240°C, head die temperature 250°C,
rotation speed, 20rpra). After repeating extrusion 10 times, test pieces were made using this combination using an injection molding machine (cylinder temperature 240°C, nozzle temperature 25°C).
0℃, injection pressure 475Kg/cj).

A light resistance test was conducted using the obtained test piece using a high-pressure mercury lamp. In addition, the same tests were conducted for those extruded once and those extruded five times. The results are shown in Table 2 below.

Blend> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 Phenyl propionate dilauryl thiodipropionate 0.3 Stabilizer (see Table 2) 0.2 Table 2 Example 3 Blend> Polyethylene 100 parts by weight Ca-
Stearate 1.0 Bionate] Methanedistearylthiodipropionate 0.3 Stabilizer (Table-
3) 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 weather oven, and the time until it became brittle was measured. The results are shown in Table 3 below.

Table 3 Example 4 Blend> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil
2-trisnonylphenyl phosphite
0.2Ca-stearate 1.0
Zn-stearate 0.1 stabilizer (
(See Table 4) 0.2 The above blend was kneaded on a roll to form a sheet with a thickness of 1 mm. A light resistance test in a weather offter was conducted using this sheet. The results are shown in Table 4 below.

Table 4 Example 5 Blend> Ba-stearate 0.7Zn-stearate 0,32.6-G 3rd
Butyl-p-cresol 0.1 Stabilizer (see Table-5) 0
．． 3 The above blend was kneaded on a roll for 5 minutes at 70°C, and
A sheet with a thickness of 0.51 was prepared by pressing at ℃ for 5 minutes. Using this sheet, the residual elongation rate after irradiation for 50 hours and 100 hours was measured using a fade meter. The results are shown in Table 5 below.

Table 5 Example 6 The compounds of the present invention are also useful as light stabilizers for paints. In this example, the effect of a two-layer metallic luster paint consisting of a base coat containing a metal pigment and a transparent top coat was examined.

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 was taken and heated to 110°C while stirring to add 2g of azobisisobutyronitrile.

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. Thereafter, the mixture was stirred at the same temperature for 2 hours to prepare an acrylic resin solution with a resin solid content of 50%.

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%), 50 parts by weight of cellulose acetate butyrate resin (20% butyl acetate solution),
5.5 parts by weight of aluminum pigment (manufactured by Toyo Aluminum Co., Ltd.; Alpaste 1123N), 10 parts by weight of xylene, 20 parts by weight of butyl acetate, and 0.2 parts by weight of copper phthalocyanine blue.
The weight part was taken and used as a base coat paint.

b) Top coat paint 48 parts by weight of the above acrylic resin solution, 10 parts by weight of butoxylated methylolmelamine, 10 parts by weight of xylene, 4 parts by weight of butyl glycol acetate, and stabilizer (see Table 6)
0.12 parts by weight (0.4% based on solid content) was taken and used as a top coat paint.

A base coat paint was sprayed on the steel plate treated with the brimer 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. 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 6 below.

Table 6 [Effects of the Invention] The polymer material composition of the present invention has excellent stability, particularly light resistance, over a long period of time.

Claims (1)

[Claims] The following general formula (I
) and at least one of the compounds represented by the following general formula (II), or at least one of the compounds represented by the following general formula (II) and other It is an addition reaction product with a mixture of α-olefin compounds, and is obtained by adding 0.001 to 5 parts by weight of a polysiloxane compound having at least one repeating unit represented by the following general formula (III) in the molecule. , a polymeric material composition with improved light resistance. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In each of the above formulas, R_1 is an alkyl group. , n represents 0 or 1, and X represents the following general formula (IV), (V) or (V
Indicates any group of I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) R_2 is a hydrogen atom, an alkyl group, or an acyl group , Y represents an oxygen atom or -N(R_5)-, R_5
represents a hydrogen atom or an alkyl group. R_3 and R_4
each represents a hydrogen atom, an alkyl group or a halogen atom, and Z represents a direct bond or an oxygen atom. )〕