JPH05155853A - Aromatic carboxylic acid derivative - Google Patents

Abstract

PURPOSE:To provide the subject new compound causing virtually no bleedout, excellent in compatibility, light stabilizing and heat stabilizing effects and hydrolysis resistance, useful as e.g. a light stabilizer for organic materials. CONSTITUTION:The objective compound of formula I [R<1> is H or 1-4C alkyl; R<2> is H or methyl; R<3> and R<4> are combined to form into =CH-R<5>; or, R<3> is H and R<4> is CH2-R<5> (R<5> is phenyl, cyclohexyl, etc.); (n) is 1-4], e.g. [tris(3- cyclohexylmethyl-2,2,6,6,-tetramethylpiperidin-4-yl] 1,3,5-benzenetricarboxylate. The compound of the formula I can be obtained by ester interchange reaction between a compound of formula II and a compound of formula III in a solvent such as hexane in the presence of a basic catalyst such as lithiumamide.

Description

[Detailed description of the invention]

[Background of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic carboxylic acid derivative having a novel structure containing a piperidine group. Specifically, the present invention relates to a 2,2,6,6-tetraalkylpiperidine skeleton which is useful as a light stabilizer for various organic materials or an intermediate thereof, and which can also be used as an intermediate for pharmaceuticals, agricultural chemicals, etc. It relates to an aromatic carboxylic acid derivative containing

[0002]

2,2,6,6-tetraalkylpiperidine skeleton (so-called hindered amine skeleton) has hitherto been used.
is excellent in radical scavenging ability and is used as a light stabilizer for various organic materials such as resins. Among light stabilizers having such a hindered amine skeleton, light stabilizers for resins are described, for example, in "Latest Technology of Polymer Additives" (Yutaka Nakahara et al., CMC, 1988). As described, polyvalent carboxylic acid esters typified by aliphatic dicarboxylic acid diesters of compound (a) below, or oligomers with higher molecular weights typified by compound (b) compounds of the type

[0003]

[Chemical 2]

[0004]

[Chemical 3]

[0005]

Among these light stabilizers, the compound (a) type light stabilizer has the disadvantage of severe bleeding out from the resin, but the compound (b) type light stabilizer has less bleed-out than compound (a), and compound (b) has not only a photostabilizing effect but also a thermal stabilizing effect.

[0006] As a result of investigations aimed at finding an excellent light stabilizer, the present inventors found that it is industrially producible, has little bleeding out from the resin, and has a high light stabilizing effect and a high heat stabilizing effect. , discovered an aromatic carboxylic acid derivative having a novel structure represented by the following general formula [I], and completed the present invention.

[Summary of the Invention]

[Means for solving the problem]

<Summary> The aromatic carboxylic acid derivative according to the present invention is represented by the following general formula [I].

[0008]

[Chemical 4] [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ^R2 represents a hydrogen atom or a methyl group. ^R3
and ^R4 together represent either =CH ^- R5 ^, or R3 is a hydrogen atom and ^R4 is _-CH2 ^- R5, provided that ^R5 is , substituted or unsubstituted phenyl group or cyclohexyl group (provided that the substituent is an alkyl group having 1 to 4 carbon atoms). n
represents an integer of 1-4. ]

<Effect> The compound of the present invention can be easily produced by an esterification reaction between an aromatic carboxylic acid and 4-hydroxypiperidines, and is highly effective against organic materials, especially resins such as polyolefins. It is a compound that exhibits a stabilizing effect. In particular, the compound [I] of the present invention has a substituent such as a benzylidene group, a benzyl group or a cyclohexylmethyl group at R3 or ^{R4 ,} and is suitable for various organic materials such as resins, particularly polyethylene, polypropylene, polystyrene, and the like. Because of its excellent compatibility with polyolefins, it has little bleed-out, has an effect of improving the appearance of the target organic material, etc., and has a high light stabilizing and heat stabilizing effect. A light stabilizer having a structure in which a substituent is introduced to R ³ or R ⁴ in this way has the structure of R It also has the effect of being superior in hydrolysis resistance to structures having no substituents on ³ or R ⁴ .

[Detailed Description of the Invention] <Aromatic Carboxylic Acid Derivative> The aromatic carboxylic acid derivative of the present invention is represented by the general formula [I]. Here, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. ^R2 is either a hydrogen atom or a methyl group, both of which exhibit similar photostabilizing effects, but hydrogen atoms are preferred for manufacturing reasons.

R ³ and R ⁴ together are a benzylidene group or a substituted benzylidene group, or a cyclohexylmethylidene group or a substituted cyclohexylmethylidene group, or R ³ is a hydrogen atom and R ⁴ is a benzyl group or a substituted benzyl group, a cyclohexylmethyl group, or a substituted cyclohexylmethyl group,
You can choose either various organic materials, especially
From the point of view of excellent compatibility with polyolefin and the effect of hydrolysis resistance, R ³ and R ⁴ together are a benzylidene group or a substituted benzylidene group, a cyclohexylmethylidene group or a substituted cyclohexylmethylidene group, or R ³ is a hydrogen atom, and R ⁴
is preferably a benzyl group or a substituted benzyl group, or a cyclohexylmethyl group or a substituted cyclohexylmethyl group, etc. Among them ^, R3 is a hydrogen atom and ^R4 is a benzyl group, a substituted benzyl group or a cyclohexylmethyl group or a substituted cyclohexylmethyl group is particularly preferred. n is an integer of 1 to 4, preferably 2 or 3.

Representative examples of the aromatic carboxylic acid derivative represented by formula [I] of the present invention are as follows. note that,
These compounds will be referred to by their numbers below.

1) 3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate (Compound No. 1)

[Chemical 5]

2) 3-cyclohexylmethyl-2,
2,6,6-tetramethylpiperidin-4-yl benzoate (Compound No. 2)

[Chemical 6]

3) bis(3-benzylidene-2,2,
6,6-tetramethylpiperidin-4-yl) terephthalate (Compound No. 3)

[Chemical 7]

4) bis(3-benzyl-2,2,6,
6-tetramethylpiperidin-4-yl) terephthalate (Compound No. 4)

[Chemical 8]

5) bis(3-benzyl-1,2,2,
6,6-pentamethylpiperidin-4-yl) terephthalate (Compound No. 5)

[Chemical 9]

6) bis(3-cyclohexylmethyl-
2,2,6,6-tetramethylpiperidin-4-yl)
Terephthalate (Compound No. 6)

[Chemical 10]

7) bis(3-cyclohexylmethyl-
1,2,2,6,6-pentamethylpiperidin-4-yl) terephthalate (Compound No. 7)

[Chemical 11]

8) tris(3-benzylidene-2,
2,6,6-tetramethylpiperidin-4-yl)
1,2,4-benzenetricarboxylate (Compound No. 8)

[Chemical 12]

9) tris(3-benzyl-2,2,
6,6-tetramethylpiperidin-4-yl) 1,
2,4-benzenetricarboxylate (Compound No. 9)

[Chemical 13]

10) tris(3-benzyl-1,2,
2,6,6-pentamethylpiperidin-4-yl)
1,2,4-benzenetricarboxylate (Compound No. 10)

[Chemical 14]

11) Tris(3-cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,2,4-benzenetricarboxylate (Compound No. 11)

[Chemical 15]

12) tris(3-cyclohexylmethyl-1,2,2,6,6-pentamethylpiperidine-4-
yl) 1,2,4-benzenetricarboxylate (Compound No. 12)

[Chemical 16]

13) tris(3-benzylidene-2,
2,6,6-tetramethylpiperidin-4-yl)
1,3,5-benzenetricarboxylate (Compound No. 13)

[Chemical 17]

14) tris(3-benzyl-2,2,
6,6-tetramethylpiperidin-4-yl) 1,
3,5-benzenetricarboxylate (Compound No. 1
4)

[Chemical 18]

15) tris(3-benzyl-1,2,
2,6,6-pentamethylpiperidin-4-yl)
1,3,5-benzenetricarboxylate (Compound No. 15)

[Chemical 19]

16) Tris(3-cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,3,5-benzenetricarboxylate (Compound No. 16)

[Chemical 20]

17) tris(3-cyclohexylmethyl-1,2,2,6,6-pentamethylpiperidine-4-
yl) 1,3,5-benzenetricarboxylate (Compound No. 17)

[Chemical 21]

18) tetrakis(3-benzyl-2,
2,6,6-tetramethylpiperidin-4-yl)
1,2,4,5-benzenetetracarboxylate (Compound No. 18)

[Chemical 22]

19) Tetrakis(3-cyclohexylmethyl-2,2,6,6-tetramethylpiperidine-4-
yl) 1,2,4,5-benzenetetracarboxylate (Compound No. 19)

[Chemical 23]

As is clear from formula [I], the aromatic carboxylic acid derivative according to the present invention is a compound having basicity due to a piperidine ring in which R ¹ is a hydrogen atom, an alkyl group or an arylalkyl group, Accordingly, the aromatic carboxylic acid derivatives according to the invention may also be acid addition salts thereof. Therefore, in the present invention, the "aromatic carboxylic acid derivative"
When we say, we include the acid addition salts thereof.
Acids capable of forming addition salts with piperidine are well known, and in the present invention also, any suitable acid can be selected from among organic acids and inorganic acids. In particular,
For example, (i) organic acids such as mono- or di- or polycarboxylic acids, and (ii) inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and the like.

<Production of Compound> The phenolic compound of the present invention can be produced by any suitable method for forming bonds and introducing or forming substituents. One suitable manufacturing method is, for example, by the manufacturing method described below.

[0034]

[Chemical 24]

The aromatic carboxylic acid derivative [I] of the present invention can be obtained by transesterification reaction between the ester compound [II] and the alcohol compound [III]. In this reaction, basic catalysts such as lithium amide and sodium methoxide are used as catalysts, and hexane, heptane,
Organic solvents such as toluene and dioxane are usually used. The reaction temperature can be selected from the range of 0°C to the reflux temperature of the solvent, and the preferred reaction temperature is 50°C.
~150°C.

<Utility of compound> The compound [I] according to the present invention is useful as a light stabilizer for various organic materials or as an intermediate for producing the same, and is also useful as an intermediate for pharmaceuticals, agricultural chemicals, etc. As mentioned above.

[0037]

[Production of tris(3-cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,3,5-benzenetricarboxylate (Compound No. 16)]

3 with a Dean-Stark type cooling pipe
2.5 g (10 mmol) of trimethyl 1,3,5-benzenetricarboxylate, 8.4 g (33 mmol) of 3-cyclohexylmethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine are placed in a 00 ml reactor. ), 0.1 g (4 mmol) lithium amide and n-heptane 2
00 ml was added, and the mixture was reacted for 10 hours at the reflux temperature of the solvent (reaction temperature: 100° C.) while separating and removing the methanol azeotroping with n-heptane. After completion of the reaction, 150 ml of diethyl ether was added to the reaction solution, which was washed twice with 50 ml of water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give a pale yellow transparent viscous liquid (9.8%).
obtained g. This was purified by alumina gel chromatography (chloroform solvent) to give the target white solid 8.
4 g was obtained (92% yield).

Analytical values are as follows. ( ¹ ) Melting point 74.0°C (2) 1H-NMR( _CDCl3 ) δ [ppm] (see Fig. 1) 0.66-1.38 (m, 63H), 1.48-1.8
0 (m, 21H), 1.86-1.96 (m, 3H),
5.58 (bs, 3H), 8.87 (s, 3H)

(3) ¹³ C-NMR (CDCl ₃ ) δ
[ppm] (See Fig. 2) 26.3, 26.5, 27.9, 32.0, 32.2,
33.2, 33.3, 33.5, 34.2, 36.3,
40.1, 43.8, 49.5, 53.3, 72.5,
132.0, 134.2, 164.7 (4) IR (KBr) wave number [cm ^-1 ] (see Fig. 3) 2922, 2848, 1725, 1447, 1377,
1332, 1242, 1153, 1018, 978, 9
49,740

Example 2 [Preparation of tris(3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,2,4-benzenetricarboxylate (Compound No. 9)] Example 1 , instead of trimethyl 1,3,5-benzenetricarboxylate, 2.5 g (10 mmol) of trimethyl 1,2,4-benzenetricarboxylate was added to 3-cyclohexylmethyl-4-hydroxy-2,2,6, 3-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine instead of 6-tetramethylpiperidine8.
9.7 g of a slightly yellow viscous liquid was obtained in the same manner as in Example 1 using 2 g (33 mmol). This was purified by alumina gel chromatography (chloroform solvent) to obtain 8.1 g of the target white solid (yield 90%).
%).

Analytical values are as follows. ( ¹ ) Melting point 69.1°C (2) 1H-NMR ( _CDCl3 ) δ [ppm] 0.88-1.58 (m, 42H), 1.80-2.1
1 (m, 6H), 2.57-2.90 (m, 6H),
5.18-5.25 (m, 1H), 5.35-5.45
(m, 2H), 6.99-7.29 (m, 15H),
7.75-7.83 (m, 1H), 8.19-8.26
(m, 1H), 8.45 (bs, 1H)

(3) ¹³ C-NMR (CDCl ₃ ) δ
[ppm] 27.3, 27.5, 30.7, 30.8, 31.2,
31.4, 32.4, 32.6, 32.9, 33.1,
33.7, 33.9, 34.0, 34.2, 34.4,
40.2, 40.4, 40.5, 49.0, 49.1,
49.3, 49.9, 50.0, 52.9, 53.1,
53.2, 71.9, 72.1, 125.8, 126.
0, 128.4, 128.7, 128.9, 129.
2, 131.9, 140.3, 141.0, 164.
3, 165.7

Example 3 [Preparation of bis(3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate (Compound No. 4)] In Example 1, 1,3,5-benzene 1.9 g (10 mmol) of dimethyl terephthalate instead of trimethyl tricarboxylate and 3-benzyl-4-hydroxy instead of 3-cyclohexylmethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine. -2,2,6,6-tetramethylpiperidine 5.4
6.5 g of a faintly yellow viscous liquid was obtained by the same operation as in Example 1, using 1 g (22 mmol). This was purified by alumina gel chromatography (chloroform solvent),
5.6 g of the target white solid was obtained (yield 90%).

Analytical values are as follows. ( ¹ ) Melting point 60.9°C (2) 1H-NMR( _CDCl3 ) δ [ppm] 1.11-1.53 (m, 28H), 1.78-1.8
7 (m, 2H), 2.03-2.12 (m, 2H),
2.66-2.76 (m, 2H), 2.87-2.96
(m, 2H), 5.15-5.21 (m, 2H), 7.
02-7.27 (m, 10H), 8.17 (s, 4H)

(3) ¹³ C-NMR (CDCl ₃ ) δ
[ppm] 27.1, 30.6, 33.1, 33.4, 34.6,
40.7, 49.0, 50.2, 52.9, 71.5,
126.1, 128.5, 128.8, 129.7, 1
34.4, 140.5, 165.2

Example 4 [Preparation of 3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate (Compound No. 1)] In Example 1, trimethyl 1,3,5-benzenetricarboxylate 2.7 g of methyl benzoate instead of
(20 mmol) to 3-cyclohexylmethyl-4-
3-benzyl-4-hydroxy-2,2, instead of hydroxy-2,2,6,6-tetramethylpiperidine
Using 5.4 g (22 mmol) of 6,6-tetramethylpiperidine, the same operation as in Example 1 was performed to obtain 7.9 g of a slightly yellow viscous liquid. This was purified by alumina gel chromatography (chloroform solvent) to obtain 6.5 g of the desired product as a colorless transparent viscous liquid (yield 92%).

Analytical values are as follows. (1) ¹ H-NMR( _CDCl3 ) δ [ppm] 1.09-1.49 (m, 14H), 1.75-1.8
4 (m, 1H), 2.03-2.11 (m, 1H),
2.66-2.77 (m, 1H), 2.85-2.93
(m, 1H), 5.11-5.17 (m, 1H), 7.
02-7.27 (m, 5H), 7.46-7.63
(m, 3H), 8.07-8.11 (m, 2H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 26.9, 30.4, 33.2, 33.5, 34 .8,
40.8, 49.0, 50.5, 52.9, 70.8,
126.0, 128.5, 128.6, 128.9, 1
29.5, 130.7, 133.0, 140.6, 16
6.1

Example 5 [Preparation of tetrakis(3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,2,4,5-benzenetetracarboxylate (Compound No. 18)] Implementation In Example 1, instead of trimethyl 1,3,5-benzenetricarboxylate, 2.5 g (8 mmol) of tetramethyl 1,2,4,5-benzenetetracarboxylate was added to 3-cyclohexylmethyl-4-hydroxy-
instead of 2,2,6,6-tetramethylpiperidine,
Using 8.2 g (33 mmol) of 3-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
By the same operation as in Example 1, 10.3 g of a slightly yellow viscous liquid was obtained. This was purified by alumina gel chromatography (chloroform-hexane mixed solvent) to obtain 9.0 g of the target white solid (yield 92%).

Analytical values are as follows. ( ¹ ) Melting point 75.1°C (2) 1H-NMR( _CDCl3 ) δ [ppm] 0.88-1.62 (m, 56H), 1.79-2.1
0 (m, 8H), 2.59-2.88 (m, 8H),
5.29-5.49 (m, 4H), 7.07-7.30
(m, 20H), 7.99-8.17 (m, 2H)

(3) ¹³ C-NMR (CDCl ₃ ) δ
[ppm] 27.2, 27.4, 31.2, 31.5, 32.5,
32.6, 32.9, 33.0, 33.1, 34.0,
34.3, 40.2, 49.2, 49.5, 49.9,
50.1, 53.0, 53.1, 53.4, 72.7,
126.0, 128.5, 128.9, 129.0, 1
35.3, 140.8, 165.1

Example 6 [Preparation of tris-3-benzylidene-2,2,6,6-tetramethylpiperidin-4-yl)1,2,4-benzenetricarboxylate (Compound No. 8)] , instead of trimethyl 1,3,5-benzenetricarboxylate, 2.5 g (10 mmol) of trimethyl 1,2,4-benzenetricarboxylate was added to 3-cyclohexylmethyl-4-hydroxy-2,2,6, Instead of 6-tetramethylpiperidine, 3-benzylidene-
Using 8.1 g (33 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 9.7 g of a pale yellow viscous liquid was obtained in the same manner as in Example 1. This was purified by alumina gel chromatography (chloroform solvent) to obtain 7.8 g of the desired product as a colorless transparent viscous liquid (yield 87%).

Analytical values are as follows. (1) ¹ H-NMR( _CDCl3 ) δ [ppm] 1.15-1.78 (m, 42H), 2.02-2.1
1 (m, 3H), 5.78-5.85 (m, 1H),
5.93-6.05 (m, 2H), 6.68 (s, 1
H), 6.75 (bs, 2H), 7.08-7.35
(m, 15H), 7.82-7.91 (m, 1H),
8.24-8.32 (m, 1H), 8.49 (bs, 1
H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 27.3, 27.5, 30.7, 30.8, 31.2,
31.4, 33.7, 33.9, 34.0, 34.2,
34.4, 40.2, 40.4, 40.5, 49.0,
49.1, 49.3, 52.9, 53.1, 53.2,
71.9, 72.1, 125.8, 126.0, 12
7.1, 127.3, 128.4, 128.7, 12
8.9, 129.2, 131.9, 136.8, 13
7.0, 140.3, 141.0, 164.3, 16
5.7

Example 7 [Preparation of tris(3-benzyl-1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,4-benzenetricarboxylate (Compound No. 10)] In Example 1, instead of trimethyl 1,3,5-benzenetricarboxylate, 2.5 g (10 mmol) of trimethyl 1,2,4-benzenetricarboxylate were added to 3-cyclohexylmethyl-4-hydroxy-2,2, 6,6-
3-benzyl-4 instead of tetramethylpiperidine
-Hydroxy-1,2,2,6,6-pentamethylpiperidine 8.6 g (33 mmol) was treated in the same manner as in Example 1 to obtain 10.6 g of a pale yellow viscous liquid. This was purified by alumina gel chromatography (chloroform-hexane mixed solvent) to obtain 8.4 g of the desired product as a colorless transparent viscous liquid (yield 89%).

Analytical values are as follows. (1) ¹ H-NMR( _CDCl3 ) δ [ppm] 0.99-1.56 (m, 39H), 1.82-2.1
0 (m, 6H), 2.24 (s, 3H), 2.28
(s, 6H), 2.55-2.92 (m, 6H), 5.
19-5.25 (m, 1H), 5.35-5.47
(m, 2H), 6.99-7.33 (m, 15H),
7.75-7.86 (m, 1H), 8.22-8.27
(m, 1H), 8.43 (bs, 1H)

(2) ¹³ C-NMR (CDCl ₃ ) δ
[ppm] 20.9, 21.1, 27.3, 27.5, 30.7,
30.8, 31.2, 31.4, 32.4, 32.6,
32.9, 33.1, 33.7, 33.9, 34.0,
34.2, 34.4, 40.2, 40.4, 40.5,
49.0, 49.1, 49.3, 49.9, 50.0,
52.9, 53.1, 53.2, 71.9, 72.1,
125.8, 126.0, 128.4, 128.7, 1
28.9, 129.2, 131.9, 140.3, 14
1.0, 164.3, 165.7

##EQU1## In addition, the substitution of the above compounds in general formula [I]
The substituents are collectively shown below. Examples Compounds_{1 2 3 4 5} ^{No. No. R R R R R n} 1 16 HHH-CH₂-R⁵ -C₆H.₁₁ 3 29HHH-CH₂-R⁵ -C₆H.₅ 3 34HHH-CH₂-R⁵ -C₆H.₅ 2 4 1 HHH-CH₂-R⁵ -C₆H.₅ 1 5 18 HHH-CH₂-R⁵ -C₆H.₅ 4 68HH=CH-R⁵ -C₆H.₅ 3 7 10 CH₃ HH-CH₂-R⁵ -C₆H.₅ 3

Application Example [Evaluation of Light Stabilizing Effect and Heat Stabilizing Effect] To 100 parts by weight of polypropylene powder having an intrinsic viscosity of 1.9 as measured in tetralin at 135° C. and isotactic content of 98%, tetrakis [3-(3,5-di-t-butyl-4
-Hydroxyphenyl)propionyloxymethyl]methane 0.1 parts by weight, calcium stearate 0.0
5 parts by weight were blended, and Examples 1 to 7 were used as additive compounds.
0.2 parts by weight of each of the compounds prepared in 2. was added and thoroughly mixed with a mixer.
It was melt-kneaded and granulated by a diameter extruder. The obtained pellets were compression-molded at 230° C. into a sheet having a thickness of 0.5 mm to prepare a test piece. Of the composition of the above test piece,
Poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl} was substituted for the compounds prepared in Examples 1-7.
{(2,2,6,6-tetramethyl-4-piperidyl)
imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}] (compound (b), manufactured by Ciba Geigy Co., Ltd., trade name CHIMASSORB944), except for using the above test piece It was made into a sheet by the same method as above and used as a test piece for comparison.

65/XW manufactured by Atlas Co., Ltd.
Using a WR type xenon weather-o-meter, light irradiation was performed at a black panel temperature of 80° C., and the light stabilization effect was compared by the time required for each test piece to deteriorate. Also, using an STD type gear oven manufactured by Toyo Seiki Co., Ltd., the thermal stabilization effect was compared at 150° C. with the time required for each test piece to deteriorate.
The results obtained were as shown in Table 1.

[0060] _{Table 1 experiment Photodegradation time Thermal degradation time} No. Added compound [hr] [hr] 1 None 120 680 2 Poly[{(6-1,1,3,3-tetramethyl (thylbutyl)imino-1,3,5-tria gin-2,4-diyl} {(2,2,6, 6-tetramethyl-4-piperidyl)imi 470 790 no} hexamethylene {(2,2,6,6- tetramethyl-4-piperidyl)imino}] (Compound (b)) 3 tris(3-cyclohexylmethyl-2, 2,6,6-tetramethylpiperidine-4 580 1260 -yl) 1,3,5-benzenetrical Boxylate (Compound No. 16) 4 tris(3-benzyl-2,2,6,6- Tetramethylpiperidin-4-yl) 1, 570 1100 2,4-benzenetricarboxylate (Compound No. 9) 5 bis(3-benzyl-2,2,6,6-te tramethylpiperidin-4-yl)tereph 550 980 Talate (Compound No. 4) 6 3-benzyl-2,2,6,6-tetramethyl Thylpiperidin-4-yl benzoate 480 810 (Compound No. 1) 7 tetrakis(3-benzyl-2,2,6, 6-tetramethylpiperidin-4-yl) 690 1160 1,2,4,5-benzenetetracarboxy Sylate (Compound No. 18) 8 tris(3-benzylidene-2,2,6, 6-tetramethylpiperidin-4-yl) 480 800 1,2,4-benzenetricarboxylate To (Compound No. 9) 9 tris(3-benzyl-1,2,2,6, 6-pentamethylpiperidin-4-yl) 670 1180 1,2,4-benzenetricarboxylate To (Compound No. 10)

[0061]

INDUSTRIAL APPLICABILITY As described above in the section [Summary of the Invention], the novel compounds according to the present invention have the ability to stabilize organic compounds against light and are easy to produce.

[Brief description of the drawing]

BRIEF DESCRIPTION OF THE FIGURES FIG. 1: Tris(3-cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl) 1,3,5-benzenetricarboxylate (Compound No. 16) prepared in Example 1. ¹ H-NMR spectrum.

FIG. 2 is a ¹³ C-NMR spectrum (proton decoupling method) of the same compound.

FIG. 3 is an IR absorption spectrum of the same compound;

Claims (1)

[Claims] 1. An aromatic carboxylic acid derivative represented by the following general formula [I]. [Chemical 1] [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ^R2 represents a hydrogen atom or a methyl group. ^R3
and ^R4 together represent either =CH ^- R5 ^, or R3 is a hydrogen atom and ^R4 is _-CH2 ^- R5, provided that ^R5 is , substituted or unsubstituted phenyl group or cyclohexyl group (provided that the substituent is an alkyl group having 1 to 4 carbon atoms). n
represents an integer of 1-4. ]