JPS58173157A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent light resistance, by incorporating a polymer obtd. by polymerizing an unsaturated compd. having a specified substd. piperidyl group. CONSTITUTION:A (co)polymer (or its hydrogenated product) obtd. by polymerizing an unsaturated compd. having a 2,2,6,6-tetramethylpiperidyl group of the formula [wherein R1 is hydrogen, oxygen, alkyl, acyl; R2 is hydrogen; R3 is hydroxyl group (R2 and R3 may be combined together to form a single bond) n is 0,1]such as 2,2,6,6-tetramethyl-4-vinyl-1,2,5,6-tetrahydropyridine, is used as a stabilizer. 0.001-5pts.wt. said polymer is blended with 100pts.wt. synthetic resin such as polyolefin or vinyl chloride resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a synthetic resin composition with improved light resistance, a polymer or copolymer of a specific unsaturated compound having a 2,2,6,6-titramethylpiperidyl group. 1, or a hydride thereof to improve light resistance≠
The present invention relates to a synthetic resin composition.

A combination of polyethylene, polypropylene, AB]1tlJ1, and polyvinyl chloride is generally sensitive to light exposure and deteriorates due to its effects, causing discoloration or a decrease in Fi strength, and cannot withstand long-term use. It is known.

Therefore, in order to prevent the deterioration of the unitary unit due to this light, Reiji,
Various stabilizers have been used in the past, but the stabilizing effect of conventionally used light stabilizers is insufficient, and the stabilizers themselves are unstable against heat or liquefaction, or are susceptible to water. Many of them are easily extracted from the polymer by #cutting, and furthermore, many of them give a skin color to the polymer, which makes it impossible to stabilize the monomer for a long period of time.

Among these conventionally used light stabilizers, hindered piperidine compounds are themselves non-shielding and have special properties such as acting not as ultraviolet absorbers but as quenchers. It has received particular attention in recent years.

However, conventionally known piperidine compounds have insufficient photostabilizing ability, have high elasticity, are extracted locally from the polymer by water, or have poor compatibility with the polymer. However, it also had disadvantages such as causing bloom etc.

In order to overcome these drawbacks, the use of high-molecular hindered piperidine compounds has recently been attempted.

For example, JP-A-52-125608 discloses a polymer of hindered piperidyl vinyl ether, and JP-A-52-141,885 discloses a polymer such as polyester having a hindered piperidyl group. , JP-A-54-21489 and JP-A-54-7118
Publication No. 5 discloses a (meth)acrylate combination of hindered piperidyl Ji4i, and JP-A No. 55-1
Publication No. 57612 discloses a maleic acid ester-olefin copolymer having a hindered piperidyl group.

However, when these polymers are used, although the volatility of the stabilizer is reduced, many have poor water resistance due to having ether bonds or ester bonds, and their stabilizing effect is not sufficient, and the stabilizing effect is not sufficient. It has the disadvantage of poor compatibility with polymeric substances and causes plumes, etc.
It was necessary to improve the dryness.

As a result of intensive studies in view of the current situation, the present inventors have determined that the above-mentioned The present invention was achieved by discovering that all of the drawbacks of the above can be overcome.

The present invention contains 0.001 to 5 parts by weight of a homopolymer or copolymer of a compound represented by the following general formula (1), or a hydride thereof, per 100 parts by weight of a synthetic resin. The present invention provides a stabilized synthetic resin composition comprising:

(In the formula, R1 represents a hydrogen atom, an oxygen radical, an alkyl group, or an acyl group, R2 represents a hydrogen atom, R5 represents a hydroxyl group, and R2 and R5 together represent a single bond. , nFiO or 1) Below, the composition of the present invention will be described in detail.

In the compound represented by the general formula (1) used in the present invention, the alkyl A group represented by R1 is:
For example, methyl, ethyl, propyl, improvil, butyl, amyl, hexyl, -butyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl, benzyl, phenylethyl, 2-hydroxyethyl, 2-hydroxypropyl, -Hydroxyethyl, 2
．． 3-Epoxyprobyl, etc. are opened, and -acyl groups such as acetyl, propionyl, butyroyl, acryloyl, methacryloyl, octanoyl, benzoyl, etc. are opened.

Therefore, representative examples of the compound represented by the general formula (1), which is used as an intermediate raw material for the (co)electrolyte used as a light stabilizer in the present invention, include the compounds shown in Table 1 below. In addition, Shishi-1 Among these compounds represented by the above general formula (1),
A compound in which R2 is a hydrogen atom and R5 is a hydroxyl group is 2,
2,6,6-tetramethyl-4-piperidone or 1
-Substituted-2,2,6,6-titramethel=4-piperidone can be easily synthesized by reacting with vinylmagnesium bromide or allylmagnesium bromide, and R2 and R5 together form a single bond. The corresponding compound in which R2 is a hydrogen atom and R
It can be easily synthesized by dehydrating a compound in which 5 is a hydroxyl group. Compounds in which R1 is a group other than a hydrogen atom can also be easily prepared by reacting a corresponding compound in which R1 is a water atom with an alkyl halide, formalin, peroxide, peroxide, or acyl halide. :Can be synthesized.

Next, a synthesis example of the compound represented by the general formula (1) shown in Table 1 will be shown.

Synthesis Example 1 2.2,6.6-tetramethyl-4-hydroxy-4-
Synthesis of vinylpiperidine (Table 1, Mu1 compound) Gold maple magnesium 46.5f, 20% vinyl bromide-
Tetrahydrofuran solution 25? Then, a temperature of 0.01F was taken, and the temperature was cooled to DC under a stream of nitrogen gas.

I stirred it from scratch. While stirring at 0°C, 1000 f of a 20% vinyl-tetrahydrofuran solution was added dropwise, and after the addition was completed, the mixture was stirred at 0°C for 1 hour and at 5-10°C for an additional 50 minutes. To this was added 77.5 t of C2,2,6,6-tetramethyl-4-piperidone, stirred for 1 hour under reflux, and after cooling, added 500 t of saturated ammonium chloride aqueous solution and
After stirring for 7 minutes, 30% NaOH aqueous solution was added to make it strongly basic. Then, take the organic layer, remove the solvent,
The obtained powder was recrystallized from n-hexane to -C melting point 58~
Product as white powder at 60°C 65. St is arrogant.

As a result of infrared spectroscopic analysis, this product was 920 cm-', 1
0! +5cm and 50803-1 had absorption due to vinyl groups, and the results of the elemental analysis shown below confirmed that they were the desired product.

Elemental analysis C(4) H(4) N←) Measured value 72.02 11.57 7.5
8 Calculated value 72.15 11,48 7
．． 65 (as C11H21NO) Synthesis Example 2 2.2,6.6-tetramethyl-4-vinyl-1,2゜5.6-titrahydrobiridine (Table 1, Mu2 compound)
Synthesis of Compound 14.6 obtained in Synthesis Example 1 Taking f, p-) luenesulfone WR21,5t and toluene 50-,
The mixture was heated and stirred for 4 hours while removing water azeotropically. After cooling,
A 20% NhOH aqueous solution (100%) was added to make it strongly basic.

Next, the organic layer was taken and the solvent was removed under reduced pressure to obtain a liquid product. This was dissolved in THFlso- and treated with Celite to obtain a pale yellow liquid product.

As a result of infrared spectroscopic analysis, this product had absorption based on conjugated diene at 1600 cm-1 and 1640 css-'', and it was confirmed that it was the desired product based on the results of elemental analysis shown by Mayuji.

Elemental analysis C (To) H (Mi) N (I) #
j constant value 79.90 11.57 8.5
5ir calculated value 80. flo 11.52
8.48 (as C11H19N) Synthesis Example 3 1.2,2,6.6-bentamethyl-4-hydroquino-
Synthesis of 4-vinylpiperidine (Clothing-1, 5 compounds on sale) 18.3t of the compound obtained in Synthesis Example 1 was dissolved in 57% formalin f6+&17.02, and the concentration was 88% at 50-600.
A total of 10.4 f. After the dropwise addition was completed, the mixture was stirred under reflux for 10 hours. After cooling, pour into 20 liters of NaOH Mizunuma Neri 100-, separate the formed solid, wash with water, and dry to give a melting point of 68~
11 growth of white powder bed at 71℃ 19. I got Of.

As a result of infrared spectroscopy, this product was found to be 2800Cσi'-
There are two sharp absorptions near 1 due to >N-CH31=,
Next, we confirmed that it was the desired product based on the results of elemental analysis.

7c elementary analysis C (1) H (hook N (movement 41j constant E 1 75.21 1
1.62 7.06d “nose i
ys, 1o 11.6B y, 11
(012H2, [)) Synthesis Example 4 Synthesis of 1.2,2,6.6-bentamethyl-4-vinyl-1゜2.5.6-titrahydropyridine (Table 1, A4 compound) Synthesis Example 5 Good compound obtained 109. 15.4 t of p-toluenesulfonic acid and 40 ml of toluene were taken and heated and stirred for 4 hours while removing water azeotropically. After cooling, 20%
NaOH water fi4 solution 5o- was added to make it strongly basic. The organic layer was then distilled under reduced pressure to a boiling point of 94°C/IS mH.
A slightly yellow liquid product of f was obtained.

As a result of infrared spectroscopy, this product was found to be 161h”1 and 1
660 cwt-1 has absorption by a conjugated diench,
In addition, the following elemental analysis confirmed that it was the target substance.

Elemental analysis C (9) H (Aspiration N (I) Measured value 80.38 11,80 7.82 Calculated value 80.45 11.73 7.82 (C12H2
1N) Synthesis Example 5 2.2,6.6-butramethyl-4-hydroxy-4-
Synthesis of allylpiperidine (Table 1, 45 compounds vI/J) To a solution of 145.3f allylmagnesium bromide and 500d of tetrahydrofuran was added 7Ju to 46.5f' of 2,2,6.6-tetramethyl-4-piperidone. The mixture was stirred under reflux for 2 hours. After cooling, 300% of saturated ammonium chloride aqueous solution was added and stirred for 50 minutes, then 50% Na
A 200% OH aqueous solution was added to form a base pillar. Then,
The organic layer was taken and the solvent was removed [1].The obtained powder was recrystallized with n-hexane to obtain a white powder product 55.29.

As a result of infrared spectroscopy, this product was found to be 1640tqn"'
There is a sharp absorption due to vinyl groups, and 3500ffi
-1 had a wide range of absorption due to hydroxyl groups, and the results of the elemental analysis shown below confirmed that it was the desired product.

Measured value 72.95 11.79 7.07ti
Calculated value of t 73.10 11.68 7.11 (C
12) as 125NO) Synthesis Example 6 2.2.6.6-tetramethyl-4-allyl-1°2.
5.6-Titrahydropyridine (Table-1, A6 compound)
Synthesis of Compound y, 9t, p-)luenesulfonic acid 11? obtained in Synthesis Example 5 Then, 50 sd of toluene was taken, and the mixture was heated and stirred for 4 hours while removing water azeotropically.

After cooling, 50% of a 20% NaOH aqueous solution was added to make it strongly basic. Next, Yukai Jd was taken, and after removing the bathing medium under reduced pressure, it was treated with Celite to obtain a pale yellow liquid product.

As a result of infrared spectroscopic analysis, the absorption of this product around 3300 cmL disappeared, and it was confirmed that the product was the desired product based on the results of elemental analysis shown below.

Elemental analysis C (a) ■(1) N (a) Measured value 80.52 1L84 7. '64It
Calculated value 80.45 11.7! l 7.82 (
C12) as 121N) Synthesis Example 7 1,2,2,6.6-bentamethyl-4-hydroquine-
Synthesis of 4-allylpiperidine (Table 1, &7 Compound m>) Compound 11.8t' obtained in Synthesis Example 5 was N-methylated in the same manner as in Synthesis Example 5 to obtain a pale yellow liquid product. Ta.

As a result of infrared spectroscopic analysis, this product had two sharp absorptions due to >N-CI (,) near 2800 rm'', and it was confirmed that it was the target product based on the results of elemental analysis shown below.

Elemental analysis C (4) H (1) N (%) 6i1j ``tai'' self c 75.8
2 11.94 15.57It:JI
I11 73.93 11.8
5 6.64 (as C15M25NO) Synthesis Example 8 Synthesis of 1.2,2,6.6-bentamethyl-4-allyl-1°2.5.6-ketone hydropyridine (Table 1, 48 compounds) Synthesis Example 7 Compound 4.6f obtained with p-toluenesulfonic acid 5.8? Then, 50 d'i of toluene was added, and the mixture was heated and stirred for 20 hours while removing water azeotropically. After cooling, 20%N
Add 60- of aOH aqueous solution and remaining salt 2a! It was made i-sexual. Next, take the first layer, remove the solvent, and evaporate under reduced pressure to reduce the boiling point to 10.
A product was obtained as a slightly yellow liquid at 0°C/13agmHgO.

As a result of infrared spectroscopic analysis, the absorption by the hydroxyl group at 5500α disappeared, and from the results of the elemental analysis shown below, it was determined that this product was the desired product.

Measured value 80.72 12.05 7.25 meter nose @ 80,84 11.92 7°25 (C1
3H23N) Synthesis Example 9 2.2,6,6-titranoter-4-allyl-1°2.
5.6-tetrahydropyridine-1-mexyl (Table 1
, &9 compounds) 5.6t of the compound obtained in Synthesis Example 6, 20Tq of sodium tungstate, 20rILt of methanol, and 3
A 0% aqueous hydrogen peroxide solution was taken and stirred for 24 hours in a room. Potassium carbonate was added to saturate the mixture while cooling with water, and the mixture was stirred at room temperature for 2 hours.

Next, the reaction solution was extracted with ether and the solvent was removed to obtain a pale orange liquid product.

This product was analyzed by ultraviolet spectroscopy.
There was an absorption of -0., and from the results of elemental analysis shown in the following (2), it was confirmed that it was the desired product.

Elemental analysis C H The coalescence may be a homopolymerization of the unsaturated compound represented by the general formula (1), a copolymer with other copolymerizable small saturated monomers, or an aqueous compound thereof. For example, the unsaturated compound represented by the general formula (1) The unsaturated compound represented by 1) (and other unsaturated monomers) is anionically polymerized, or polymerized using a single peroxide or azonitrile compound as an initiator, and then hydrogenated as necessary. Can be synthesized.

Other unsaturated monomers that can be used in the present invention include, for example, ethylene, propylene, butene-1, isobutylene, hexene, octene, decene, totycene, tetradecene, hexadecene, oftatecene, eicosene, styrene, α-methyl-styrene, cyclohexene, Butadiene, vinyl chloride, acrylonitrile, methyl vinyl ketone, methyl vinyl ether, vinyl acetate, acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, butyl acrylate, methyl methacrylate, dimethyl maleate, diethyl maleate, maleic acid diptyl,
2゜2.6,6-teto2methyl-4-piperidyl-vinyl ether, 1,2,2,6.6-bentamethyl-4-
Piperidyl-vinyl ether, 2,2,6.6-tetotsumethyl-4-piperidyl-allyl ether, 1.2,
2,6,6-bentamethyl-4-piperidyl-allyl ether, 2,2,6,6-tetramethyl-4 acrylate
-piperidyl, acrylic acid-1+2.2゜6.6-bentamethyl-4-piperidyl, 8,8,10.10-tetramethyl-9-ab-3-ethyl-1,5-dioxaspiro[S,S:]- 6-un1 methyl acrylate, methacrylic acid-1,2゜2.6.6-pentamethyl-4-piperidyl, maleate bis(1,2,2,6,
6-bentamethyl-4-piperidyl), bisfumarate (
1,2,2,6,6-bentamethyl-4-piperidyl)
, bis(81”lν.

10.10-Pentamethyl-9-aza-5-ether-1
, 5-dioxaspiro[s,s]-s-ranylmethyl)fumarate 6 g.

The molar ratio of the compound represented by the general formula (D) and the other unsaturated monomer is selected from the range of 10:0 to 1:9.

The (co)monomerized unsaturated compound represented by the general formula (1) used in the present invention has a molecular weight of 50
0 to 10,000 is preferred.

Representative examples of the (co)polymer of the compound represented by the general formula (1), which is used as photostable-11 in the present invention, are shown in Table 2 below.

Next, a specific synthesis example of the (co)polymer of the compound represented by the general formula (1) used in the present invention will be shown.

Synthesis Example 1 Synthesis of homopolymer (Table 2, Stabilizer D) of lI & 4 compound (Table 1) 1.7 m of dry tetrahydrofuran 10- and 15% butyllithium hexane solution was taken and placed in A4 under a nitrogen gas stream.
Compound 3.6f was added dropwise. After the addition, the mixture was stirred at room temperature for 7 hours. Next, the reaction solution was poured into 200 methanol, and the resulting precipitate was separated from P and dried to obtain a white powder product.

The softening point of this product is 145-155℃, the molecular weight is 1,
It was 750.

Synthesis Example 11 Homopolymer of Mu4 Compound (Table-1) (Table-2, Stabilizer E
) Synthesis of A4 compound 4. Of, dicumyl peroxide 0.04
F and 6 d of toluene were taken and stirred under reflux for 6 hours. Next, after removing the toluene, 60ml of tetrahydrofuran was added, and the mixture was poured into 200ml of methanol filtered through Celite.
The produced Fled body was separated from P and dried to obtain a white powder product. This product had a softening point of 215-225°C and a molecular weight of 4.500.

Synthesis Example 12 Stable reduced go hydride (Table 2, Stable@F) C) Synthesis Polymer obtained in Synthesis Example 11 1. Dissolve the sodium in 10 d of hydrofuran (2 d), add 2 d of ethanol, 0.1 f of 5-palladium-carbon, and place in an autoclave.
It was heated to 150° C. for 6 hours under a hydrogen pressure of 180 K4/−.

Next, the reaction solution was filtered through celite and poured into 100 methanol to obtain a white powder product. The softening point of this product is 215-225°C, and the molecular weight is 4500-4600.
Met. Furthermore, as a result of NMR analysis, it was confirmed that the double bond had disappeared.

The present invention is for improving the light resistance of a synthetic resin by adding a homopolymer or copolymer of an unsaturated compound represented by the general formula (1), or a hydrated product thereof to a synthetic resin. The amount added is usually o, o o t to 5 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of synthesis-9.
It is 3 parts by weight.

Invention 1: *- Examples of the synthetic resins to be improved in light resistance include α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-5-methylbutene, or ethylene-vinyl acetate copolymers; Polyolefins such as ethylene-propylene copolymers 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-ethylene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer Combined, vinyl chloride-styrene-anhydrous! Leic acid terpolymer, vinyl chloride-styrene-7
Acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic Acid ester copolymer, vinyl chloride-maleate ester copolymer, tx chemical engineering nyl methacrylate ester copolymer, vinyl chloride-acrylonitrile copolymer, herogen-containing synthetic resin such as internally plasticized polyvinyl chloride, petroleum resins, coumaron resins, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers,
Acrylic ester-butadiene-styrene copolymer,
Methacrylic acid ester-butadiene-styrene copolymer, methacrylate such as polymethyl methacrylate) 4H
1. Ho! j Vinyl alcohol, polyvinyl formal,
Mention may be made of polyvinyl butyral, linear boris ester, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, HL cellulose resin, or phenolic resin, urea resin, meladen resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. can. Further, rubbers such as imprene 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 by peroxide or radiation, and foamed polymers such as foamed polystyrene foamed by the foaming side.

By further adding a phenolic antioxidant to the composition of the present invention, the oxidative stability can be improved. Examples of these phenolic antioxidants include 2
, 6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octoxyphenol, stearyl-(S
, S-di-methyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-,5,
5-di-tert-butylphenyl)propionate, distearyl-5,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4.6-)lis(5').

♂-di-5-butyl-4'-hydroxybenzylthio)
-1,5,5-) riazine, distearyl (4-hydro*C-S-mef-5 J15 butyl)benzyl aronate, 2,2-methylenebis(4-methyl-6-5-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 coglycol ester,
4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-5-butylpheno-A/),2. /-ethylidene bis(
4-Sec-butyl-6-tert-butylphenol), 1,1
．． 3-) Lis(2-methyl-4-hydro, dPx--
tert-butylphenyl)butane, bis[2-5-butyl-
4-methyl-6-(2-hydroxy-3-11,5]f
5-methylbenzyl)phenyl terephthalate,
1,3.5-)lis(2,6-dumedel-3-hydroxy-4-tert-butyl)benzyl isocyanurate), 1,
5.5-Tris(5,5-di-tert-butyl-4-hydroxybencyl)-2,4,6-) listylbenzene, tetrakis[methylene-5-(S,S-di-tert-butyl-
4-Hydroxyphenyl)propionate comethane, 1
, 3.5-) lis(5,5-di-5-5-butyl-4-hydroxybenzyl) isocyanurate, 1,5.5-1 lis((5$5-di-5-butyl-4-hydroxyphenyl)propionyl [oxyethyl] isocyanurate, 2-octylthio-4,6-di(4-hydroxy-3
, 5-di-tert-butyl) phenol, 5.5-triazine, 4. ! - Phenols such as thiobis(6-5-butyl-m-cresol) and carbonic acid oligoesters of 4,4-butylidenebis(2-tert-butyl-5-methyl 7'enol) (e.g. polymerization [2=5*' e
5 p 6-7 v 8 #9.

Examples include polyhydric phenol carbonate oligoesters such as 10).

Composition C of the present invention: It is also possible to further add a sulfur-based antioxidant to improve its oxidative stability. These sulfur-based antioxidants include, for example, dialkylthiocyclobionates such as dilauryl, diolistyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl. Examples include esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate (eg, pentaerythritol tetralaurylthioptetrabionate).

By further adding a phosphorus-containing compound such as phosphite to the composition of the present invention, a compound that improves light resistance and heat resistance can be obtained. Examples of the containing compound include trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl-diphenyl phosphite, tris(2,4-di-5-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl)
Phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1s 1 #
'5-) Lis(diphenyl in 2-methyl-5-tert-butyl-4-hydro)butane diphosphite, tetra(0
12-15a alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-
4,4'-butylidene bis(5-methyl-6-tert-butylphenol) diphosphite, tris(5,5-di-tert-butyl-4-hydro-diphenyl) phosphite,
tris(mono-dimixed nonylphenyl) phosphite,
Hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl)/bi-5-butylphenol)]111,6-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'-iso7'0pylidene bis(
2-5th butylphenol)] phosphite, phenyl diisodecyl phosphite, cy(nonylphenyl)pentaerythritol diphosphite, tris(1,s-
di-stearoyl (diisopropyl) phosphite F,
'*'-Isoptetrapylidene bis(2-5th butylphenol) cy(nonylphenyl)phosphite, 9.10
- G8 Hydro9 - Oxer 10-7 Male 7 Affenance Lane - 10 - Oxide, Nato 2I? (2,4-
Examples include di-tert-butylphenyl)-4,4-pyphenylene diphosphonite.

By adding other light stabilizers to the composition of the invention, its lightfastness can be further improved. Examples of these light stabilizers include 2-hydroac-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Hydroxybenzophenones such as benzophenone, 2-(2'-
and dorogoshi (-1-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2-(/-hydroxy-13-di-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5-methylphenyl)penztriazole, 2-(2' Benzotriazoles such as -hydroxy-3',5'-sheet-t-amylphenyl)benzotriazole, phenylsalicylate), pt-butylphenylsalicylate, 2,4
-di-t-butylphenyl-3,5-di-t-butyl-
4-Hydroxybenzoate, hexadecyl-5,5-
Benzoates such as di-t-butyl-4-hydroyacibenzoate, 2,2'-thiobis(4-t-octylphenol) Nl salt, [2,2'-thiobis(4-1
-octylphenolate))-n-butylamine Ni
Nickel compounds such as -(se s-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, α-cyano-I-methyl-β-(p-methodiphenyl)acrylic methyl substituted acrylonitriles such as N-2-ethylphenyl-d-2-ethoxy-5-tert-butylphenyl oxalic acid diamide), N-2
-Ethylphenyl-attached -2-ethoxyphenyl oxalic acid dianilides.

In addition, if necessary, the composition of the present invention may contain heavy metal deactivators, nucleating agents, metal soaps, organotin compounds, plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, grooves, etc. It can include machining, machining assistance, etc.

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

Example 1 Polypropylene 100]
Stable cutting of L amount part (Table s) 0.5 A press sheet with a thickness of 0.5 m was prepared using the above formulation, and a light resistance test was conducted using a high-pressure mercury lamp. Also 80℃
A light resistance test was also conducted on the sheet after being immersed in hot water for 15 hours. The results are shown in Table-3.

Table 3 Example 2 It is known that the effect of normal O-stable cutting is gradually lost due to volatilization, decomposition, etc. during high-temperature processing of resin.

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

According to the following formulation, the resin and additives were mixed in a mixer for 5 minutes, and then a powder was prepared using an extruder. (Cylinder temperature WIL 250℃, 240℃, head die salt [2
After extrusion was repeated 5 times at 50° C. and rotational speed zorpm, test pieces were made using an injection molding machine using this compound.

(Cylinder temperature: 240° C., nozzle temperature: 250° C., injection pressure: a 7 s Ktt/cd) Using the nine test pieces obtained, a light resistance test was conducted using a high-pressure mercury lamp. 9. The same test was carried out on the one extruded once. The results are shown in Table 4.

Blend> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate
0.2 *i1 part stearyl β-5.5-di-tert-butyl-4-0,1 hydroxyphenylglobionate di9lylthiodiglobionate 0.
2 stable stiffness (Table-4) 0.2 table
-4 Polyethylene 1001
- Stearate 1.0 Tetrakis [methylene-5-(s,s-di-5-butyl-4-hydroxyphenyl)p 0.10 Bionate] Methanedistearylthiodipropionate 0.3 Stable cutting (Table-
s) o.2 The above blend was mixed and pressed to create a sheet of rhinoceros O*5sm. 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-5.

Table-5 Example 4 Ethylene-vinyl acetate copolymer-100!1tlH2,
6-G 5th butyl/I/-p-cresol 0.1Ca-
Stearate 0.1 Zn-Sterate 0.1 Diisodecyl phenyl phosphite 0.2 Stable cutting (Table 6
) 0.2 Roll 150 of the above formulation
After crosstalk at C, press sheet (thickness 0.4 om) at 140℃
)It was created. Place this sheet in a weather oven for 5o.
.

The residual rate of anti-aggressive power after time irradiation was measured. Table 6 shows the results.
Shown below.

Table 6 Example 5 Polyvinyl chloride 100 Parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Trisnonylphenyl phosphite 0.2 Ca-stearate 1
．． 0 Zn-stearate 0.1 Stabilizer (Table 7) 0.3 The above mixture was mixed on a roll to form a sheet with a thickness of 1 inch. A light resistance test in a weather offter was conducted using this sheet. The results are shown in Table-7.

Table 7 Example 6 ABS resin 100 parts by weight 4
．． 4'-Butylidene bis(2-50,1-butyl-m-
Cresol) Stabilizer (Table 8) 0.5 The above mixture was kneaded with a roll and then pressed to form a sheet with a thickness of 5 cm.

Using this sheet, the tensile strength remaining after 800 hours of irradiation was measured using a weatherometer. The results are shown in Table-8.

Table 8 Example 7 Polyurethane resin (Asahi Denka 1!U-1oo) 1o
o East 1iNB&-Stepplate
0.7 Zn-stearate 0.5 2.6-di-tert-butyl-p-cresol 0.1
Stabilizer (Table 9) 0.5 The above blend was kneaded on a roll at 70°C for 5 minutes and pressed at 120°C for 5 minutes to form a sheet with a thickness of 0.5 mm. The remaining elongation rate of this sheet after 30 hours of irradiation was measured using a total fade meter.

The results are shown in Table-9.

Table 9 Continuation of page 1 0 shots Akira Ryoji Kimura Ade, 5-2-13 Shirahata, Urawa City Within Ka Argus Chemical Co., Ltd.

Claims (1)

[Scope of Claims] Per 100 parts of synthetic resin, 0.0 parts of a homopolymer or copolymer of a compound represented by the following general formula (1), or a hydride thereof, is added. , 001-5 A stabilized synthetic resin composition containing violet parts. (In the formula, R1 represents a hydrogen atom, an oxygen radical, an alkyl group, or an acyl group, R2 represents a hydrogen atom, R5 represents a hydroxyl group, or R2 and R5N - together represent a single bond, and n represents a single bond. (Indicates 0 or 1.)