JPS6267072A - 2,2,6,6-tetramethylpiperidylamide of substituted carboxylic acid and photostable polymer composition stabilized therewith - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to derivatives of 2,2,6,6-titramethylpiperidine, and more particularly to novel compounds, namely 2,2,6-thitramethylpiperidine derivatives of substituted carboxylic acids. .6-titramethylpiperidylamide and photostable polymer compositions stabilized thereby.

These compounds are stabilizers for polymeric compounds used for example in the production of polymeric films for greenhouses, chemical complexes, polymeric materials used in the production of injection molded articles (transfer components, unit tubes). It can be used as an agent.

[Conventional technology]

Most part-molecular materials have low stability to ultraviolet effects. As a result, they deteriorate quickly and thus lose their usefulness.

In order to provide a photostable composition based on polymeric materials, special cooling agents, or photostabilizers, are introduced into the composition. These additions should have high photostabilization efficiency.

Currently, o-hydroxybenzophenone (US ['F1!c
? U.S. Pat. No. 3,641.213) and 0-hydroxybenzo) IJ azole derivatives (U.S. Pat.
, 824.192; FRG% Permit No. 2.45
5, 155) is used as a light stabilizer for polymeric materials. However, these photostabilizers have low photostabilization efficiency.

In recent years, sterically hindered amine derivatives, in particular derivatives of 2.2.6°6-titramethylpiperidine, such as 2°2.6.6
Esters of -tetramethyl-4-hydroxy-piperidine and carboxylic acids (see FRG Percentage No. 1.929.928 and No. 2.258.752) can be made from polymeric materials (polyethylene, polypropylene, It is widely used as a light stabilizer for polystyrene, polyvinyl chloride, polyamide, etc.).

Among them, the practical application is the product name [Tinupin (Tinupin)].
uvin) 770 J known as bis-(2*2
*Produced by 6*6-tetramethyl-4-piperidinyl) sebacate (Modern Plas
tics, 1975.

No. 5, 32). The photostabilization efficiency of these compounds is
It is significantly higher than the photostabilization efficiency of 0-hydroxybenzophenone and 0- and droxybenzotriazole derivatives. However, these compounds also do not guarantee a sufficiently long service life of polymeric materials under conditions of intense solar radiation.

[Problem that the invention seeks to solve]

The present invention relates to the provision of new light stabilizers for polymeric materials that may have follow-up light stabilization efficiency.

The compounds according to the invention are new and hitherto unknown in the literature.

[Means for deciding the problem]

2.2 of novel compounds according to the present invention, namely substituted carboxylic acids
．． 6.6-Titramethylbiperidylamide has the following general formula (where n is 1 or 2, n is 1, and n is 2), then A is OH1, m is 1 or 2, and f-).

The compound according to the invention is a white crystalline material with a melting point of 82-230'C and is resistant to aliphatic alcohols and chlorinated hydrocarbons.

Their structures were determined by IR spectroscopy, elemental analysis and molecular U
Confirmed by analytical data.

A π:stable polymeric composition comprising a polymer and a light stabilizer comprises a substituted carboxylic acid of the formula 2.2,6.
6-titramethylpiperidylamide in the following component proportions (
Heavy voltage width) Polymer 99.0-99.95
Contains in.

Known polymers such as polyolefins (high and low density polyethylene, polypropylene and copolymers thereof), polystyrene and copolymers thereof, polyvinyl chloride, polyamides, polyurethanes, etc. can be used as polymers.

In order to improve the thermal stability of the light-stable polymer composition according to the present invention, it is desirable to also include a thermal stabilizer of 0.05 to 0.3 4 Fr in the polymer.

As thermostabilizers, generally known types of stabilizers are used, such as sterically hindered phenol derivatives (for example, the tetraester of 3°5-tert-4-hydroxyphenylpropionic acid and pentaerythritol [
Irganox 1010];
3,5-di-tert-butyl-4-hydroxyphenylpropionic acid or octadecyl ester (Irganox 1076); 2,2'-methylene-bis-(
4-Methyl-6-tert-butylphenol) (AO
-2246): Phosphite (for example, tree (p-
nonylphenyl)-phosphite [Polyguard (Pol
Compounds selected from the following may be used:

In order to enhance the photostabilizing effect, it is preferred that a UV absorber is also incorporated into the photostable polymer composition at a weight of 0.1 to 0.3. As ultraviolet absorbers, 0-hydroxybenzophenone derivatives [for example, 2-hydroxy-4-octyloxybenzophenone: cyasorb (O
yasorb) OV 531 ] and ]0-hydroxypenzotriazole 2-(3',5'-di-tert-butyl-7,'-hydroxyphenyl)-5
-Chloropenzotriazole: Tinupin (Tinuvi)
n) 327 ], 2- (2'-hydroxy-5'-
Methylphenyl)-benzotriazole (tenupin P)
But it can be used.

2.2.6 of light stabilizers, i.e. rji-substituted carboxylic acids.

The needles of 6-tetramethylbiperidylamide, as well as heat stabilizers and UV absorbers, are limited, on the one hand, by the achievement of a maximum stabilizing effect and, on the other hand, by the economic efficiency of the composition.

The polymeric materials stabilized by the compounds according to the invention can be used in almost all kinds of articles, such as films, fibers, bars, etc.

[Effect]

Photostable polymer compositions stabilized by 2.2.6.6-titramethylpiperidylamide of substituted carboxylic acids according to the present invention are characterized in that their photostability differs from that of 0-hydroxybenzophenone and 0-hydroxybenzophenone. 1.5 to 4 times better than photostable polymer compositions stabilized by triazole derivatives and based on the ester of 2.2.6.6-tetramethyl-4-hydroxypiperidine and carvone 0 to 15% better than the composition. Furthermore, 2.2 of the substituted carboxylic acids according to the present invention
, 6.6-Tetramethylbiperidylamide has a thermal stabilizing effect in polystyrene plastics.

The method for preparing substituted carboxylic acid 2,2,6,6-titramethylpiperidylamide, as well as the photostable polymer compositions stabilized thereby, is simple, uses standard equipment, and follows the steps below. can be converted to real I in the following manner.

The method for producing compounds according to the present invention involves converting compounds or their lower esters to 2.2 to 2.2% at an ambient temperature of 170 to 210°C while simultaneously distilling off the generated lower alcohol or water.
6. Based on the known reaction of amidation with 6-tetramethyl-4-aminopiperidine (triacetone diamine) (Pagan Dohilgetag, "The Practical Method in Organic Chemistry", "Kimya", Baplishers, Moscow, 19
68, pp. 445, 454). The desired product is removed by recrystallization from an organic solvent.

The photostable polymer composition is prepared by semi-industrial methods. The light stabilizer is introduced into the polymer at either the )° coalescence production stage or the processing stage into an article. This is done using any marking equipment (extruder, mill, injection molding machine).

The light stabilizers can be incorporated either individually or in the form of a solution or suspension in the corresponding solvent or dispersant.

UV absorbers as well as pA stabilizers may be introduced both at the polymer production stage and at its processing stage.

〔Example〕

For a better understanding of the invention, a specific example of Wakako is provided below by way of illustration.

Example 1 In a 100 ml three-necked flask equipped with a stirrer, thermometer, descending heat of cooling, Wurtz backing and receiver,
) 15.62 g of N-cyclohexylaminoacetic acid ethyl ester and 18.39 g of ethyl ester of N-cyclohexylaminoacetic acid were charged and the
Heating at a temperature within the range of 0-210°C. After cooling the reactants, the product is recrystallized from toluene and melts at 83°C.
2. of the desired product, namely N-cyclohexylaminoacetic acid.
2,6,6-tetramethylbiperidylamide (I) (
CttHss) iso) gives 25.1 g (85th coefficient of the theoretical kja value when calculated for 9 lyacetone diamine).

Elemental composition: 01. H33N,O molecular weight calculation value: 0
69.11, Hls, 26, N 14.23 295.
47 Actual 1 value%: C68,98,) 111.56,
N 14.08 290.7 IR spectroscopy data: VC, Q (amide I) am 1665 cm-'; δk
lH (amide II)w1510cm-';'NH""
3360 cm 0 Example 2 2°2.6.
6-titramethylpiperidylamide (') in Example IK above.
Triacetone diamine 15.62 according to the method described
g and N-morpholinoacetic acid ethyl) 17.28
Obtained from g. The yield of the desired product was 26.24 E (9% of the theoretical value calculated for triacetone diamine).
It has a melting point of 103°C (toluene).

Elemental composition: 01s'z嘗N, 02 Molecular weight 1; 1
Calculated value %: c 63.57, H10,31, N 14.
82 283.42 tllllj value%: C63,7
4, H10,28, N 14.48 317.8 IR spectroscopic analysis data 0=CI(amide 1)-1685cm-'HδNH(
7mid II) ms 15150m-”;1/NH
-33850n.

Example 3 The compound of this example, namely N-piperidinoacetic acid, had a 2°2.6.
6-titramethylpiperidylamide (tri) was treated with triacetone diamine 6 in a manner similar to that described in Example 1 above.
2.5 g and ethyl N-piperidinoacetate) 6
Produced from 8.34 g. The yield of the desired product was 90.
74 g (80.6% of the theoretical value when calculated on 74g), and the melting point is 77°C (
toluene).

Elemental composition: C111H31'30 Molecular weight meter value: 068.28.1111.10. N 14.
93 281.45 Actual measurement value: c 68.61, H1
0,91,N 14.83 280.4IR spectroscopy data: νc,,o(amide I)-1680am-1
; δHa (amide II)-1510Cm-'; v
HHwm3375 Cm-”.

Example 4 The compound of this example, namely 2,2,6°6-titramethylpiperidylamide (rV) of anilineacetic acid, was prepared from 23.44 g of triacetone diamine and 26.8 g of anilinoacetic acid ethylate according to the method described in Example 1. generate,.

The yield of the desired product was 35.7 g ()! 82.2% of the theoretical value when calculated for J acetone diamine)
and the melting point is 175°C (isopropanol).

Elemental composition: C17H2? N30 Calculated molecular weight%
: (! 70.55, H9,401IN 14.52
289.4 actual value excellent: 070.34, H9,96, N
14.68 282.5 IR spectroscopic analysis data Niji c
-o(amide I)-1655cm-'; δNH(amide I'!)81500 Ca1l-1; l/H
H”3390,3440 (4m 0 Example 5 The compound of this example, namely piperazine N,N'-bis(
2,2,6,6-titramethylpiperidyl)acetamide (V) is prepared from 31.25 g of triacetone diamine and 25.75 g of N,Nl-piperazinodiacetic acid diethylate according to the method described in Example 1 above.

The yield of the target product was 37 g (77.3% of the theoretical value when totaling 1 t based on triacetone diamine),
The melting point is 230°C (toluene).

Yuan composition: C'26H5ON11°2 Molecular weight meter 111 [im%]: C65.23, H10.5
3, N 17.55 478.7 Actual value: O
65,30, H10,60, N 17.78 472.
5 Engineering R spectroscopic analysis data “C,O (amide I)-16
50c+n-'; δNu (amide II)-1530
an-1,1500am-'; v, -53350c
m-5゜Example 6 The compound of this example, 2,2,6,6-titramethylpiperidylamide (Vl) of N-cyclohexylaminopropionic acid, was treated with triacetone diamine in a manner similar to that described in Example 1. 31.25 g and 37.05 g of N-cyclohexylaminopropionic acid methylate. The yield of the desired product is 53.4 g (86.4% of theory, calculated on lyatone diamine) and the melting point is 122°C.

Elemental composition: CraH3sNsO molecule) Calculated width: C
69,85, H11,40, N 13.58 309.
5 Actual value%: G 69.55, H 11,32, N 1
3.43 308.21R spectroscopic analysis data:'(40
(Amide I)-1670 cm-''; δNH (amide u)=1560 em-' i WHH-3240
,33200m-'.

Example 7 The compound of this example, i.e. piperazine, N,Nl-bis-
(2,2,6,6-Tetramethylbiperidyl)-propioamide (1) was prepared in a manner analogous to that described in Example 1 with 31.25 g of triacetone diamine and N.

N1-Piperazino dipropionic acid dimetate 25.8
Generated from g. The yield of the desired product was 34.4 g ()
The theoretical value of 6 when calculated for ria-7tondiamine
8%) and has a melting point of 161°C (toluene).

Original non-composition: O, H54N, 02 Molecular weight meter A value%
: C66,36, H10,74, N 16.58 5
06.78 Actual value%: C66,64, H10,71
, l'l 16.01 502.3 IR spectroscopy data: Ray. (amide I) ml, 650an-'Hδ volume (amide ■) 1530 bi1; plate-3330,34
00 mouth f1゜Example 8 Compound of this example, 2,2,6,6-tetramethylbiperidylamide (■) of ljD chibe/dylaminopropionic acid
is prepared from 46.9 g of triacetone diamine and 58 g of benzylaminopropionic acid methylate according to the method described in Example 1 above. The yield of the desired product was 73.
14 g (76.8% of theory calculated on triacetone diamine), with a melting point of 132° C. (toluene).

Elemental composition 019H31N30 Calculated molecular weight range: c n, 88, !19.84, N 13.24
317.5 Actual value %: 071.92, ) 19.68
, N 13.71 318.5 Spectroscopic analysis data:
'co(amide I) #1660 am-1.

'IJH(amide[)i565cm, siNH-
3330 (4m.

Example 9 The compound of this example, namely 2.
2,6,6-Tetramethelpiperidylamide (IX) was filtered from 15.62 g of triacetone diamine and 17.32 g of N-morpholinopropionic acid methylate according to the method described in Example 1 above. The yield of the desired product is 1 for 27 g ()
90.8 range of the theoretical value of spring), and the melting point is 82
°C (isopropanol).

Elemental composition: 016"31N302 Molecular weight calculation: C64,61, H10,51, N 14.1
3 297.4 central 6 river i ■ %: c 64.4
5, H10,26, N 14.22 29L
5IR spectroscopy data Niji. . (amide 1)-16
30(to)-1;'Nu (amide old-1510Cm-
'; VHH-3450, 3270cm-'.

Example 10 The compound of this example, namely 2.
2,6,6-Tetramethylbiperidylamide (X) was prepared by the method described in Example 1 and similar to 181 from 31.25 g of triacetone diamine and 34.20 g of N-piperidinopropionic acid methylate. generate,.

The yield 11 of the desired product is equal to 29.3 g (49.6% of theory, calculated on triacetone diamine) and the melting point is 133° C. (hexane).

Elemental composition: C17Hss Ns O molecular weight *+4r
J I16%: C69,111H11,26
, N 14.22 295.47) Good! 6111
Ip%: C69.47, 1d11.84,
l'+ 14.63 298.3 IR spectroscopic analysis data Niji (j) (amide I) - 1630 cm-1
;'NH(7<If)-1520am-1; NH-3400. 3250 am-”.

Example 11 Illegal compound, R[Ichi2', 2', 6', 6'
-7) 7. )'2,2,6°6-tetramethylbiveridylamide (xl) of nalpiperidylaminopropionic acid
) is prepared in a manner analogous to that described in Example 1 from 31.25 g of triacetone diamine and 8.6 g of methyl acrylate. The yield of the desired product was 29.33 g (total of 11 sheets per methyl acrylate, the theoretical value of 8
0) and has a melting point of 139°C (ethyl acetate).

Elemental composition: C21H42N4” Molecular weight %: C68.80, H11.55, N 15.2
8 366.6 Actual value%: C68,75, Hll, 6
2, N 15.47 365.8 IR spectroscopic analysis data
: 'c,o(amide I)-1660cm-';J
NH (amide II) #m1510 cm-1;
14H-3260, 3435 CDD-'.

Example 12 The compound of this example, i.e. 2.2°6.6-
Citramethylpiperidylamide (Xfl) Y produced from 15.21 g of phenoxy acid and 15.62 g of triacetone diamine according to the method described in Example 1. The yield of the desired product was 24.5 g (84.3% of the total weight of 7% based on lyacetone diamine), and the melting point was 85° C. (toluene).

Elemental composition: (+tHzaNzOz calculated molecular weight %: 070.31, H9.02, N 9.65
290.41 Actual aill value%: 069.91, H8
, 9m, N 9.48 307.01R spectroscopic analysis data "'080 (amide I) W1670 am-1;
'N)i (7mid II) m 1500 Cm-'
; V NHm 3290 Cm″″1° 1113 Unexamined compound J1, 2,2°6 of phenylthioacetic acid.
6-titramethylpiperidylamide□GJI) f/l
I 1 from 15.62 g of triacetone diamine and 20.6 g of phenylthiornic acid ethylate. The charge of the target organism a is 23
．． 25 g (75.9% of theory calculated on 1 chloride amine) and has a melting point of 94°C (
Hexane) Elemental composition: C'+7"211 rays 280 Molecular lid i'it JNlm %: e 66.62,)1
8.55, N 9.14, 306.47810.46 1ull +#%: 0 66.35,
)1 8.61, N9.08, 303.4
810.23 IR spectroscopy data: l'c,o(7mido I)-16
80cm.

JNH (amide II) -1505cm-'r
'N11m3420.3220 cm-'.

Example 14 The compound of this example, namely 2,2,6,6-tetrametherbiveridylamide (xIv) of n-tert-butylphenoxyacetic acid, was prepared using triacetone in the same manner as described in Example 1 above. Diamine 15.62 F and n-tert
23.7 g
Generate from. Yield of target product -1+, is 19.9 g
(The theory K when calculated for triacetone diamine
m(1) 57.4%), and the melting point is 88°C (
hexane).

Elemental composition: C21H42202 molecular weight meter nm %:
072.79, H9,89, N 8.08 346
．． 52 Actual value%: 072.70, H9,94, N 8
．． 08 349.10IR spectroscopic analysis data Niji CXO
(amide 1)-1685CIIl-'; δNH (Avado II)-1530am''''; v, (H-3
430cm-'.

Example 15 The compound of this example, bis-(2,2,6,6-tetramethylpiperidylacetamide)-2',2'-phenoxypropane (XV), was prepared using triacetone diamine 15. 52 g and 18.42 g of 4,4'-phenyloxypropionic acid dieterate
Generated from g. The yield of the desired product was 27.6 g (
) and a melting point of 79°C (gasoline/toluene).

Elemental composition: C3F H56N404 Calculated value % of molecules: C71.58, H9.09, N 9.02
620.88 Reality %: C7], 44, H9,
13, N 8.86 627.00 IR spectroscopy data Niji. -8 (amide I) m 1670 cm-'
; δ (amide II) # 1520 Cm-'
; ShiN, =-3430,3270am-'.

hi Example 16 The compound of this example, namely β-(21, zl, sl,
2,2,6,6-tetramethylbiveridylamide (X
VI) i Produced in a manner analogous to that described in Example 1 from 65.07 g of acetate mether and 7156.26 g of triacetone diamide. The yield of the desired product was 115.3 g (61.01 g of theory calculated on lyacetone diamine), and the melting point was 20
It's 2 degrees Celsius (Inpropa Tools).

Elemental composition: O, H421440 molecule Calculated value %: c
69.79, H11,18, N 14.80 378
．． 61 measured value: 069.94, H11,20,N
14.70 388. OIR spectroscopy data” '0.0
(7mid I)-1680 cm-'; δNH (amide n)-a 1520 cm-'; y m
3400 cm-', -H 1640 cm 0 Example 17 2.2゜6 of 21, 21, 61, 61-tetramethylpiperidylaminopropionic acid, commonly understood as acetone
．． 6-Tetramethylpiveridylamide (Compound XI)
Introduce 0.3 parts by weight of powdered polypropylene into the 99.71M unit. The resulting mixture is stirred while the acetone is evaporated, then introduced into a laboratory mixer and treated therein for 30 minutes. As a result, uniformity was left behind,
Then) 8I 120μm film at 210±2°
Compression molding at a temperature of C. The film was then placed in a weatherproof cabinet and subjected to Xθnotetest 1.
Subjected to photooxidative aging at 200°C. The degree of destruction of the film is evaluated in an IR spectrometer as the time it reaches a carbonyl index equal to 0.3.

According to the method described above, a light-stable polymer film was obtained using other light stabilizers according to the invention (compounds

The photostabilizing agent of the present invention was evaluated firstly by the conventional stabilizers, namely Tinuvin 327 and Tinuvin 77.
0 and shear soap υv-s31 are prepared in a similar manner.

The results of the corresponding tests 7 below are shown in Table IK.

Table 1 (11fit part) (hr) 1 Tinuvin 327 0.3 130
2 Sea Soap υV-5310, 32103 Chinupi:
y 770 0.05 2404 Tinuvin 770 0.1 3805 Tinuvin: y770 0.3 5006 Tinupin 770 1.0 6507 Compound XI O, 052758 Compound XI
O,1420 9 Compound XI O,3530 10 Compound XT 1.0 72011
Compound X ■ 0.1 46012 Compound *
Xll O,362513 Compound X! 1
1.0 75014 Compound XI) 0
．． 1 42015 Compound XIV O,
354516 compounds = xrv 1.0 76
017 Compound XV O, 0531018 Compound XV O, 3540 19 Compound XV 1.0 780 Table 1 above
The data given for compounds M, XI, heavy and x
The photostability of the polypropylene film stabilized with UV-531 was about 2.5 times better than that of the film stabilized with [Tinuvin 7F0], and The photostability of the film is about ls
It has been proven that the percentage is higher.

Example 18 2°2.6. of phenoxyacetic acid dissolved in ethanol.
6-tetramethylbiperidylamide (compound XI) 0.
1 part by weight is introduced into 99.9 parts of powdered high density polyethylene. From the resulting mixture, ethanol is removed in a vacuum cabinet. As a result, a homogeneous material is obtained, from which a film with a thickness of 100 tm is compression molded under a pressure of 150 kg/Cm'' at a temperature of 160 °C.

The film is subjected to photooxidative aging in a weathering device Xenotest 150. IR by time and elapsed time of their destruction to reach a carbonyl index of 0.3.
Evaluate with a spectrometer.

According to this method, other light stabilizers according to the invention (compounds ■, ■, ■, K, Also used to produce photostable polymer films.

The results of the corresponding tests are shown in Table 2.

Table 2 1 Shear soap UV-5310, 19751, To
.

2 Shea Soap UV-! 31 0, 3 1
．． 250 2,5003 Tinuvin 770 0
,05 1. Zoo 1.9004 Tinuvin 7
70 0,15 1,550 2.8955
Tinuvin 770 0.3 1.850 3.3
506 Tinuvin 770 1.0 2.100
3.9007 Compound Punishment 0.15 1,7
50 3.2508 Compound XV O,32
,0503,7009 Compound Store 0,3 1.
795 3.3601O compound M 1.0
2,420 4.50011 Compound n
O,051,2302,10012 Compound I
O,31,9953,68513 compound 1
0,5 2.070 3,88514 Compound III 0605 1,250 2.1
5515 Compound 0.1 1,695
2.47516 Compound 1 1,0 2
．． 360 4,29517 Compound Title 0,
1 1,710 3.20018 Compound ■
0,3 2,100 3.68519 Compound K O,11,7203,34020 Compound K O,52,0003,58021 Compound XI O,31,9203,380 The data given in Table 2 above indicates that Compound 1, I , ■, K, Q
The photostability of a film of low density polyethylene stabilized with It has been demonstrated that the photostability of the film is about lo% better than that of the film.

Example 19 0.05 parts by weight of 2,2,6,6-titramethylpiperidylamide of N-cyclohexylaminopropionic acid (compound W) dissolved in acetone was added to the phenol heat stabilizer Irganox 1010 (1 part by weight of 0.2). and 99.75 parts by weight of powdered polypropylene. The resulting mixture is mixed to evaporate the acetone, then loaded into a laboratory mixer and treated there for 30 minutes.

As a result, a homogeneous product is obtained, passed through a laboratory extruder at a temperature of 210-220° C. (depending on the zone) and granulated. The granules are melted in sector 17 of the laboratory fiber forming apparatus.
Prepare it.

The die-extruded single filament is cooled in a water bath at a temperature of 18-20°C and then subjected to a 4-fold drawing at a temperature of 130°C. The obtained monofilament with a linear density of 8 tex (xenotes) 1200
Subjected to photo-oxidative destruction in a medium. Increased the degree of breakage of single filament to 40
They retain their tenacity after 0 hours of irradiation, evaluated by the value (%).

According to the method described above, monofilaments were produced using other light stabilizers according to the invention (Compound Technology, ■, v, M, X, ■, XV) and using another heat stabilizer Irganox 1076. Ru,.

To evaluate the photostabilization efficiency, fibers stabilized by Irganox 1010 along with Tinuvin 327 and Tinuvin 7 FuO are produced in a similar manner.

The test results are shown in Table 3 below.

Table 3 1 Tinuvin 327 0.3 20.0 Irganox 1010 0.21 L sword/Tsuku+A
1υlli IJ+U, l) The data shown in the above Cloth 3 are based on the compound 1. TV, V, %I, X
, the photostability of the fibers stabilized by
4 times better, and about 15 times better than fibers stabilized with Tinuvin 770.

Example 20 2.2,6. of n-tart-butylphenoxyacetic acid.
6-tetramethylpiveridylamide (compound XIV) 0
．． 2 parts by weight of shear sieve UV-531 (
0.2 parts by weight) and AO2246 (0.05 parts by weight)
Introduced together with. The polymer composition is prepared at a roll temperature of 160° C. while the web is continuously cut for 10 minutes.

From the mixed web of polymer, 2 mm plates are compression molded at a temperature of 160±2° C. and two-sided samples are cut from them. Place the sample in a weatherproof cabinet (xenotes) 12
Photo-oxidative aging K 20,000 was applied in 00.

The degree of failure of the sample is evaluated by the relative elongation retained at breakage after aging for 20oO hours.

Photostable compositions are prepared in a similar manner using other photostabilizers according to the invention and known additives, namely Tinuvin 327, Ciasibu tJV-531 and Tinupin 770. The test results are shown in Table 4 below.

Table 4 4 Tenuvin 327 0.3 1200 hours), 0-2246 0.05 Post-destruction A
O-2246u, ua l4 Tinuvin 770 0.2 Tinuvin 327
0.2 71.5AO-22460,0
5 15 Tenubin 770 0.1 Cyanoop U'l/-5310,158,IAO-22
460,05 16 Tinupin 770 0.2 Seasoap VU-5310,278,0AO-2246
0.05 17 Tenuvin 770 0.3 Shear Soap UV-5310,388,0AO-2246
0,05 18 Tinuvin 770 0.3 Seasoap UV-5310,177,0 people 0-2246
0.0519 Tinuvin 770
0.1 Cyanuv UV-5310,367,5
AO-22460,05 20 Tinuvin 770 0.1 Tinuvin/327 0,3 62.0AO-
22460,05 21 Compound XI O,1 Cyanoop UV-5310,167,9AO-2246
0,05 22 Compounds XI O,2 Seasoap tJV-5310,288,2AO-224
60,05 23 Compound XI O,2 Tinuvin 327 0.2 82.0AO-
22460,05 24 Compound XI O,3 CyanooptJV-5310,390,t)AO-22
460,05 25 Compound XI O,3 Cyanoop UV-5310,171,9AO-2246
0,05 26 Compounds XI 0.1 Seasorb UV-5310,372,5AO-2246
0,05 27 compounds XrV O01 Tinuvin 327 0,1 56.5AO
-22460,05 28 Compound XIV O,1 Cyanoop W-5:31 0.1
60,0AO-22460・05 29 Compound XIV O,2 Shea Sheept
lV-5310,280,5AO-22460,05 The data given in Table 4 above is based on the data for Compound X according to the present invention.
The photostability of plates from low-density polyethylene stabilized with I% is about 3 times better than that of plates stabilized with Sheathorp W-531 or Tinuvin 327, and as a stabilizer It has been demonstrated that the photostability is approximately 10% higher compared to that obtained when using Tinuvin 770.

Example 21 2,2,6,6-tetromethylpiperidylamide of β-(21,21,sl,sl-tetramethylpiperidylamine)-crotonic acid (compound size: 1.01 parts,
Tinuvin 327 (0.1 parts by weight) and Irganox 1010 (0.05 parts by weight) are introduced into 98.85 parts by weight of powdered polypropylene. The resulting mixture was stirred, granulated and molded into 10 tex monofilaments according to the method described in Example 19 above, and the monofilaments were subjected to photo-oxidative aging for 500 hours in a weatherproof cabinet Xenotest 1200. attach

The photostabilization efficiency of the additives is evaluated by the strength of their retention of single filaments at break.

According to said method, other light stabilizers of the invention and known additives, namely Tinuvin 327, Sheasorp UV-531
and Tinuvin 770 to prepare and test photostable compositions.

The test results are shown in Table 5 below.

Table 5 I. Luganox 1010 0.05 Irganox 1010 0.05 Irganox 1010 0.3 Irganox 1010
0.05 Irganox 1010 0
．． 3 Irganox 1010 0.05 said light 5
The data shown in the compound according to the present invention, ■, N,
XV, monofilaments stabilized by Punishment are 2-4 times more photostable than filaments stabilized by Tinuvin 327 or Sheathorp UV-531, and about 15 times more photostable than yarns stabilized by Tinuvin 770.
% has been demonstrated to be photostable.

Example 22 N,N'-bis-(2,2,6,6-tetramethylpiveridyl)acetamidopiperazine (Compound V) 0.
1 part by weight is introduced into 99.9 parts by weight of granular impact-resistant polymethic acid. From the resulting mixture, prepare a 5% benzene solution. After complete dissolution of the high-impact polystyrene and stabilizing additives, a film having a thickness of 70 μm is produced by pouring the solution.

After evaporation of the solvent (approximately 2 days), the resulting film is subjected to photooxidative aging under non-extreme ultraviolet light. Increase the degree of destruction of the film to 100
By accumulation of carbonyl groups 1'jl (relative units) at 1720 cm-' after time aging and at 900 cm-'
11 spectrometer by the retention of the double bond (cc bond) in -' (% of initial value).

Using the method described above, using other photostabilizers according to the invention and, for comparison purposes, using a known stabilizer, namely Tinubi/P, a photostable composition vI4 is prepared.

The test results are shown in Table 6 below.

Table 6 1 Tinubi:yP 0005 8,8
152 TinubiyP O,107,4203
Tinubi:yP O,306,2304 TinubiyP
1.00 7.0 325 Compound X
I O,054,1456 Compound XI 003
0 3. Ofi97 Compound M 0010 3
．． 7 598 Compound IV'0,30 3.1
659 Compound V O,302,8801O Compound 7111 0.10 3.4 6211
Compound Vll O,054,84212 Compound X
1.00 1.7 9213 Compound X
O, 302, 782 The data presented in Table 6 show that the compounds of the present invention ■, ■, V, V■, X and It has been demonstrated that it imparts twice as much photostability to high-impact polystyrene.

Example 23 Samples of high-impact polystyrene films are prepared according to the method described in Example 22, using the stabilizer according to the invention and for comparison of stabilizing activity using a known stabilizer, namely Polyguard. to prepare a heat-resistant composition.

The film is subjected to heat aging in an air thermostat at a temperature of 120°C. The degree of failure of the film is determined as described in Example 22 after heat aging for SOO hours.

The test results are shown in Table 7 below.
N 0.10 5,0 2
93 # 0.30 5,2 31
4 1 0.50 3.4
375 N 1,00
2,9 416 Compound XI O,
053,2497 Compound V O,102,553
8 Compound XI'/ 0.30 1.9 67
9 Compound XV O,501,77710 Compound I
X 1,00 1.3 81 The data presented in Table 7 above show that compounds V, ■, M, KN and
It has been proven to be twice as effective.

Example 24 2,2,6,6-tetramethylbiveridylamide of phenoxyacetic acid (compound xi) 0. 999.5 parts by weight of a terpolymer [composition (parts by weight): styrene 54, acrylic acid nitrile 28, polybutadiene 1B] were introduced. The composition was blended in a ball mill and then 19
homogenizing in a mixer at a temperature of 0°C to 210°C;
. In this way, 91m1! From the prepared mixture, standard bars are injection molded (50X6X4M) and the bars are subjected to ex-aging under a carbon arc lamp for 200 hours. After aging, the bars are reduced in their elasticity using a pendulum hammer [kgf;/
cm” (% of initial value)].

Using the same method, photostable compositions were prepared and tested using other photostabilizers according to the invention and the known photostabilizer Tinuvin P. The results of these tests are shown in Table 8. show.

Table 8 1 Tenuvin P O,05292 Tinuvin P
O,1034 3 Tinuvin P 0050 474 Tinuvin P 1.00 505 Compound
XI O,05416 compound 1 0.10
687 Compound Xll O,5088
The data shown in Table 8 above corresponds to Compound 11 according to the present invention.
It has been demonstrated that ■,

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n is 1 or 2, and if n is 1, A
▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲Mathematical formulas, chemical formulas, There are tables, etc. ▼ ;▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; There are mathematical formulas, chemical formulas, tables, etc.▼;, and if n is 2, then A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲mathematical formulas, chemical formulas,
2,2,6,6-tetramethylpiperidylamide of substituted carboxylic acid (where m is 1 or 2). 2. A photostable polymer composition containing a polymer and a light stabilizer, which has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where n is 1 or 2, and n If is 1, then A ▲ has mathematical formulas, chemical formulas, tables, etc. ▼; ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ ; ▲ has mathematical formulas, chemical formulas, tables, etc. ▼; ▲ mathematical formulas, chemical formulas, tables, etc. There are▼; ▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲Mathematical formulas, chemical formulas,
There are tables, etc.▼; ▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲Mathematical formulas, chemical formulas,
There are tables, etc.▼; ▲There are mathematical formulas, chemical formulas, tables, etc.▼;▲Mathematical formulas, chemical formulas,
If n is 2, then A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼; ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and m is 1 or 2. 2,2,6,6-tetramethylpiperidylamide of the substituted carboxylic acid of
2,2,6,6 1.0-0.0 of 5-substituted carboxylic acid
A photostable polymer composition comprising 5-tetramethylpiperidylamide. 3. A light-stable polymer composition according to claim 2, additionally incorporating a heat stabilizer in an amount of 0.05 to 0.3% by weight of the polymer. 4. additionally containing a UV absorber in an amount of 0.1, 0.3% by weight of the polymer, claim 2 or 3;
The photostable polymer composition described in Section 1.