JPH10140089A - Benzotriazole-based ultraviolet absorber having improved durability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject absorber composition exhibiting an improved durability and a low loss on exposing the membrane thereof to chemical rays by including a specific resin such as a thermosetting acrylic melamine resin, and a specific benzotriazole. SOLUTION: This benzotriazole-based ultraviolet absorber having an improved durability consists of (A) a resin selected from a group of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxycarboxy resin, a silane-modified acrylic melamine resin, a melamine with an acrylic resin having a carbamate side chain and a melamine containing a carbamate group with an acrylic polyol resin, and (B) 0.01-5wt.% benzotriazole of the formula (G, G2 are each an electron absorbing group, G1 is H or a halogen, G2 is a halogen, nitro, etc.; R1 is H, a 1-24C alkyl, etc.; R2 is H, a 1-24C alkyl, etc.), etc., and has <=0.22 absorbance unit loss after 1200hr exposure to a xenon arc weatherometer, <=0.27 absorbance unit loss after 1500hr exposure, and <=0.40 absorbance unit loss after 2500hr exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION A benzotriazole-based UV absorber having a benzene ring substituted by an electron-withdrawing portion exhibits enhanced durability and a low loss rate when incorporated into an automotive coating.

[0002]

BACKGROUND OF THE INVENTION Benzotriazoles have long been an important part of UV absorbers and have been accepted as being commercially important in many industrial applications. The prior art is numerous about their manufacture and use. However, the demands have always been more stringent, and the demand and research continues for more stable and durable benzotriazoles.
Due to environmental concerns and the replacement of HAPS solvents with non-HAPS solvents such as esters, ethers or ketones,
HAPS solvents such as xylene are increasingly surfaced, and the demand for increased durability for automotive coatings is even more urgent. The actual place, the publication, "JL Ge
riock et al. Proc. 36th Ann
ual Tech. Sym. (Clearland
Coating Society), May 18, 1
The automotive industry is most concerned with UVA losses from automotive paints and coatings, as seen in "993".

[0003] Vyscomol Soedin, Se
r. A, 18 (3), 553 (1976) describe that hydrogen bond strength and photostability of benzotriazoles are in a linear relationship.

[0004] E. FIG. Pickett et al. ,
Angew. Makromol. Chem. 232,2
29 (1995) describes the photolysis of benzotriazole-based UV absorbers in poly (methyl methacrylate) films. Despite the substitution breaking the intermolecular hydrogen bonds that are important for stability, structural changes generally cause only slight differences in degradation rates. Pickett et al. Have not tested any benzotriazoles containing both electron withdrawing and electron donating groups as in the present invention.

The prior art has led to the conclusion that strengthening hydrogen bonds makes benzotriazoles more stable, but does not teach how to do this. Although the present invention discloses benzotriazoles that exhibit this enhanced durability, surprisingly, this enhanced durability is not always associated with greater hydrogen bond strength. In fact, compounds with enhanced durability often have weaker, less strong hydrogen bonds.

[0006] US Pat. 4,226,763; 4,
278, 589; 4,315, 848; 4,275,0
04; 4,347, 180; 5, 554, 760; 5,
563,242; 5,574,166 and 5,607,
987 describes selected benzotriazoles in which the 3-position of the hydroxyphenyl ring is substituted by an α-cumyl group, which exhibits very good stability in automotive coatings. These benzotriazoles represent the state of the art. The present invention is directed to producing benzotriazoles that exhibit greater durability and lower loss rates than the prior art benzotriazoles.

[0007] US Pat. 5,278,314; 5,
280,124; 5,436,349 and 5,516,
At 914, a red shift was performed (red-shift
d) Benzotriazoles are described. In these benzotriazoles, the 5-position of the benzo ring is substituted by a thioether, alkylsulfonyl or phenylsulfonyl moiety. Redshifting of benzotriazoles is desirable for spectral reasons. The group at the 5-position, which is also electron withdrawing, offers the additional advantages of low loss and durability found in the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention relates to benzotriazoles having enhanced durability and low loss rates when formulated into automotive coatings.

More particularly, the present invention relates to a coating composition stabilized with benzotriazole, wherein said coating composition exhibits enhanced durability and low loss rate when said benzotriazole is incorporated into said composition. (A) a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin having a carbamate side group crosslinked with melamine, or an acrylic polyol crosslinked with melamine containing a carbamate group A resin selected from the group consisting of resins, and (b) 0.01 to 5% by weight of the formula A, B, C or D based on the resin solids.

Embedded image Wherein G ₁ , G ₂ or T represents an electron withdrawing group; G ₁ represents a hydrogen atom or a halogen atom; G ₂ represents a halogen atom, a nitro group, a cyano group, R ₃ SO—, and R ₃ SO _2. −,
—COOG ₃ , CF ₃ —, —P (O) (C ₆ H ₅ ) ₂ ,
_{-CO-G 3, -CO-NH} -G 3, -CO-N
_{(G 3) 2, -N (} G 3) -CO-G 3,

Embedded image G ₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, and 5 to 1 carbon atoms.
2 cycloalkyl group, phenylalkyl group having 7 to 15 carbon atoms, phenyl group, the above phenyl group substituted by 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the above phenylalkyl group Represents; R ₁
Represents a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, C 7 -C 15 phenylalkyl, phenyl, C 1 -C 4 on the phenyl ring
Represents the above phenyl group or the above phenylalkyl group substituted with 1 to 4 alkyl groups; R ₂ represents a hydrogen atom,
A straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms,
A phenylalkyl group having 7 to 15 carbon atoms, a phenyl group, the above phenyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the above phenylalkyl group, or R ₂ Is a hydroxyl group or —OR ₄ , wherein R ₄ represents a linear or branched alkyl group having 1 to 24 carbon atoms.
_{OH, -OCO-R 11, -OR} 4, -NCO or -NH
_The above alkyl group substituted by ₂ or a mixture thereof;
Or one or more -O -, - NH- or -NR ₄ - groups or is interrupted by a mixture thereof, and unsubstituted or one or more -OH, -OR ₄ or -NH ₂ group or their Represents the above-mentioned alkyl group or the above-mentioned alkenyl group which may be substituted by a mixture of; or R ₂ represents —SR ₃ ,
Or represents -NHR ₃ or -N (R _{3) 2;} or R ₂ is -
(CH ₂ ) _m -CO-X- (Z) _p -YR ₁₅ [wherein X is-
O- or -N (R ₁₆₎ -, Y represents the -O- or -N
(R ₁₇ ) —, and Z represents an alkylene group having 2 to 12 carbon atoms, 1 to 3 nitrogen atoms, oxygen atoms or an alkylene group having 4 to 12 carbon atoms interrupted by a mixture thereof. Or a C3-C12 alkylene group, a butenylene group, a butynylene group, a cyclohexylene group or a phenylene group, each of which is substituted by a hydroxyl group, m represents 0, 1 or 2, p represents 1 or each of X and Y is -N
(R ₁₆ )-and -N (R ₁₇ ) also represent 0, and R ₁₅
Or is a group _{-CO-C (R 18) =} C (H) R 19,
When Y represents —N (R ₁₇ ) —, the group —CO together with R ₁₇
—CH ＝ CH—CO—, R ₁₈ represents a hydrogen atom or a methyl group, and R ₁₉ represents a hydrogen atom, a methyl group or —C
O—X—R ₂₀ , wherein R ₂₀ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a formula

Embedded image (Wherein, the symbols G ₁ , G ₂ , R ₁ , X, Z, m and p have the same definitions as above), and R ₁₆ and R ₁₇ independently represent a hydrogen atom, a carbon atom number of 1 Represents a C 12 -C 12 alkyl group, a C 3 -C 12 alkyl group interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or a C 7 -C 15 aralkyl group; When R ₁₆ represents an ethylene group, it together with R ₁₇ also forms an ethylene group. ]; N is 1
Or 2 and when n represents 1, R ₅ is Cl, OR
₆ or NR ₇ R ₈ or R ₅ represents —PO (O
R ₁₂ ) ₂ , —OSi (R ₁₁ ) ₃ or —OCO—R ₁₁ , or is interrupted by —O—, —S— or —NR ₁₁ — and is unsubstituted or —OH or —OCO cycloalkyl group 12 C 5 carbon atoms are substituted by unsubstituted or -OH;; alkyl group 24 to be straight or C 1 -C branched optionally substituted by -R ₁₁ not A straight-chain or branched alkenyl group having 2 to 18 carbon atoms, which is substituted or substituted by -OH,
Of 7 to 15 carbon atoms aralkyl group, -CH ₂ -
Represents CHOH-R ₁₃ or a glycidyl group; R ₆ is a hydrogen atom, unsubstituted or one or more OH, C 1 -C was straight or branched substituted by OR ₄ or NH ₂ groups of 24 Represents an alkyl group, or -OR ₆ is-(O
CH ₂ CH ₂ ) _w OH or — (OCH ₂ CH ₂ ) _w OR
_{21 wherein} w represents 1 to 12 and R ₂₁ represents an alkyl group having 1 to 12 carbon atoms; R ₇ and R ₈ independently of one another are hydrogen, 1 to 12 carbon atoms. 18 alkyl group; -O -, - S- or -NR ₁₁ - with an alkyl group having 3 to carbon atoms and straight-chain or branched interrupted 18, cycloalkyl groups having 5 to 12 carbon atoms, carbon Represents an aryl group having 6 to 14 atoms or a hydroxyalkyl group having 1 to 3 carbon atoms,
Or R ₇ and R ₈ together with an N atom represent a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring; when n represents 2, R ₅ represents a divalent group —O—R ₉ —
R ₉ represents one of O- or -N (R ₁₁ ) -R ₁₀ -N (R ₁₁ )-; R ₉ is an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, a carbon atom Formula 4 alkynylene group, cyclohexylene group, -O- or -CH
_{2 -CHOH-CH 2 -O-R} 14 -O-CH 2 -CHO
H-CH ₂ - C 4 -C straight or branched chain which is interrupted by represents 10 alkylene group, R ₁₀ is a good straight or branched chain optionally interrupted by -O- An alkylene group having 2 to 12 carbon atoms, a cyclohexylene group or

Embedded image Or R ₁₀ and R ₁₁ together with two nitrogen atoms form a piperazine ring, R ₁₄ is a linear or branched C 2 -C 8 alkylene group, —O— A linear or branched alkylene group having 4 to 10 carbon atoms, a cycloalkylene group, an arylene group or

Embedded image And R ₇ and R ₈ independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, or R ₇ and R 8
₈ together represent an alkylene group having 4 to 6 carbon atoms, 3-oxapentamethylene group, 3-iminopentamethylene group or 3-methyliminopentamethylene;
R ₁₁ is a hydrogen atom, a straight-chain or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a straight-chain or branched alkenyl group having 3 to 8 carbon atoms. R ₁₂ represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 15 carbon atoms;
Is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms,
An aryl group having 6 to 16 carbon atoms or 7 carbon atoms
R ₁₃ represents H, —PO
A straight or branched alkyl group having 1 to 18 carbon atoms, which is substituted by (OR ₁₂ ) ₂ , unsubstituted or OH
R ₃ represents a phenyl group, an aralkyl group having 7 to 15 carbon atoms or —CH ₂ OR ₁₂ ;
Is an alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
To 20 hydroxyalkyl groups, alkenyl groups having 3 to 18 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or carbon atoms The above-mentioned aryl group or perfluoroalkyl moiety substituted by one or two alkyl groups having 1 to 4 atoms is 1,1,2,2- having 6 to 16 carbon atoms;
L represents a C1 to C12 alkylene group, a C2 to C12 alkylidene group, a benzylidene group, a p-xylylene group or a cycloalkylidene group; and T represents-
_{SO -, - SO 2 -,} - SO-E-SO -, - SO 2 -
_{E-SO 2 -, - CO} -, - CO-E-CO -, - CO
O-E-OCO -, - CO-NG 3 -E-NG 3 -CO
— Or —NG ₃ —CO—E—CO—NG ₃ — (wherein, E
Represents an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an alkylene group interrupted by or terminated by a cyclohexylene group having 8 to 12 carbon atoms. ). Consisting of a benzotriazole represented by the following formula: wherein the benzotriazole loses less than 0.22 absorbance units after 1200 hours of exposure in a xenon arc weatherometer or 0.27 absorbance units after 1500 hours of exposure. It relates to compositions that exhibit enhanced durability and low loss rates when the coating is exposed to actinic radiation, as evidenced by low loss or less than 0.40 absorbance units after 2500 hours of exposure.

Preferably, component (b) is of the formula A '

Embedded image (Wherein G ₂ is a fluorine atom, a chlorine atom, a cyano group, R _{3
SO 2 -, CF 3 -,} - CO-G 3, represents -COO-G ₃ or _{-CO-N (G 3) 2} ; G 3 represents an alkyl group of 1 to 12 carbon atoms; R ₁ is A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or one or two alkyl groups having 1 to 4 carbon atoms substituted on the phenyl ring; R ₂ represents an alkyl group having 1 to 12 carbon atoms,
A phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or —CH ₂ CH ₂ COOG ₄ (wherein G ₄ is substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, to represent six -O- atom through the above which is interrupted by 1 to 6 -O- atom together are substituted by one or OH are suspended alkyl group, and R ₃ is the number of carbon atoms An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms 1 or 2
Represents the aryl group substituted by ).

Most preferably, in the compound of formula A ', G ₂
Is a fluorine atom, a chlorine atom, a cyano group, R ₃ SO ₂ —, C
F ₃ —, —COO—G ₃ or —CO—N (G ₃ ) ₂ ; G ₃ represents an alkyl group having 1 to 8 carbon atoms;
R ₁ represents a hydrogen atom, a phenyl group or an α-cumyl group;
R ₂ represents an alkyl or phenyl group having 4 to 12 carbon atoms, and R ₃ represents a phenyl group or 8 carbon atoms.
Represents 12 to 12 alkyl groups.

Particular preference is given to G in the compounds of the formula A '
₂ represents phenyl-SO _2- , octyl-SO _2- , a fluorine atom or CF _3- ; R ₁ represents an α-cumyl group or a phenyl group, and R ₂ represents a tert-butyl group or t
represents an ert-octyl group.

[0013] Preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of various substituents are as follows: When any of R ₁ to R ₂₁ is an alkyl group, such a group is, for example, a methyl group, an ethyl group, an isopropyl group. Group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, tert-amyl group, 2-ethylhexyl group, tert-octyl group, lauryl group, tert-dodecyl group, tridecyl group, n-hexadecyl group , N-octadecyl and eicosyl; when any of the above groups is an alkenyl group, such a group is, for example, an allyl group or an oleyl group; and any of the above groups is a cycloalkyl group. In such cases, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. If any of the above groups are phenylalkyl groups, such groups are, for example, benzyl, phenethyl, α-methylbenzyl and α, α-dimethylbenzyl; When any of the above is an aryl group, they are, for example, a phenyl group, a naphthyl group, or when substituted by an alkyl group, for example, a tolyl group and a xylyl group. When R ₆ is interrupted by one or more —O— groups and / or replaced by one or more OH, the —OR ₆ moiety may be, for example, — (OCH ₂ CH ₂ ) _w OH or — (OCH ₂ CH ₂ ) _w OR _{21 wherein} w represents 1 to 12 and R ₂₁ can be an alkyl group having 1 to 12 carbon atoms.

When E is an alkylene group, it is a methylene group, ethylene group, tetramethylene group, hexamethylene group, 2-methyl-1,4-tetramethylene group, octamethylene group, decamethylene group or dodecamethylene group. When E is a cycloalkylene group, it is, for example, a cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene group; and E is interrupted by or terminated by a cyclohexylene group. If so, it is, for example, a saturated diyl group derived from limonene, referred to herein as a dihydrolimonenediyl group.

Another preferred embodiment of the invention is a compound of formula C wherein R ₁ represents a tert-butyl group, n represents 1, R ₃ represents a phenyl group and R ₅
Represents —OR ₆ (wherein, R ₆ represents a linear or substituted octyl group). In yet another preferred embodiment of the present invention, wherein n represents 2, R ₁ represents a tert-butyl group, R ₃ represents a phenyl group and R ₅ represents —O—R
₉ -O- (wherein, R ₉ is -O- or -CH ₂ -CHOH
_{-CH 2 -O-R 14 -O-} CH 2 -CHOH-CH 2 -
Is an alkyl group having 2 to 24 carbon atoms interrupted by ) Is a compound of formula C. When E is an alkylene group, it is a methylene group, an ethylene group, a tetramethylene group, a hexamethylene group, a 2-methyl-1,4-tetramethylene group, an octamethylene group, a decamethylene group or a dodecamethylene group; When it is a cycloalkylene group, it is, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group and a cyclododecylene group; and when E is interrupted or terminated by a cyclohexylene group. Is, for example, a saturated diyl group derived from limonene, referred to herein as a dihydrolimonenediyl group.

When the compound of the present invention contains a carboxyl moiety (where R ₂ is --CH ₂ CH ₂ COOR
₆ (wherein, R ₆ represents a hydrogen atom). ), Alkali metal or amine salts of the above acids are also considered as part of this invention, and such UV absorbers can be used in aqueous systems due to the increased water solubility of the compounds in question.

R ₆ , R ₇ and R ₈ can be the following C 3 -C 16 alkyl groups interrupted by —O—, —S— or —NR ₁₁ — and optionally substituted by OH: : methoxyethyl, ethoxyethyl group, butoxyethyl group, blanking Toshiki propyl group, methylthioethyl _{group, CH 3 OCH 2 CH 2 OCH} 2 CH 2 -, CH 3 C
_{H 2 OCH 2 CH 2 OCH 2} CH 2 -, C 4 H 9 OCH
₂ CH ₂ OCH ₂ CH ₂ —, ethylthiopropyl group, octylthiopropyl group, dodecyloxypropyl group, 2
-Hydroxyethyl group, 2-hydroxypropyl group, 4
-Hydroxybutyl group, 6-hydroxyhexyl group,-
_{CH 2 CH 2 -NH-C 4} H 9, -CH 2 CH 2 CH 2
NH-C ₈ H ₁₇ and _{-CH 2 CH 2 CH 2 -N (} C
_{H 3) -CH 2 CH (C} 2 H 5) is a C ₄ H _9.

R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ can be the following C 5 -C 12 cycloalkyl groups:
A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclodecyl group.

R ₇ , R ₈ and R ₁₁ can be the following alkenyl groups: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.

When R ₆ is an alkenyl group, it may have the same meaning as R ₇ as an alkenyl group, R ₈ and R ₁₁ . However, it is -CH = CH _2, n- undec-10-There is also obtained in enyl or n- octadec-9-enyl group, and it is also possible to be replaced by -OH for R _6.

R ₇ and R ₈ can be the following C ₇ -C 15 aralkyl groups: benzyl group, α
-Phenethyl group, 2-phenethyl group or 4-tert-
Butylbenzyl group.

When R ₁₁ , R ₁₃ or R ₁₂ are aralkyl groups, they may independently of one another have the same meaning as R ₇ or R ₈ .

Independently of each other, R ₇ , R ₈ and R ₁₁ can be the following C 6 -C 14 aryl groups: phenyl, α-naphthyl or β-naphthyl.

When R ₇ and R ₈ are C 1 -C 3 hydroxyalkyl, they are: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

As C 2 -C 8 alkylene, R ₉ and R ₁₄ can be: ethylene, propylene, butylene, hexylene or octylene.

As an alkylene group, R ₁₀ can be the same group, but additionally can be a higher molecular weight group such as a decylene or dodecylene group.

When R ₉ is C 4 -C 8 alkenylene, the following are examples of suitable groups: butenylene.

In the case of R ₉ and R ₁₄ , suitable groups of straight-chain or branched C 4 -C 10 alkylene groups interrupted by —O— are as follows: —CH ₂ CH ₂ OCH ₂
CH ₂ —, —CH (CH ₃ ) —CH ₂ —O—CH ₂ —C
_{H (CH 3) -CH 2 CH} 2 OCH 2 CH 2 OCH 2 C
H ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂
OCH ₂ CH ₂ -.

When R ₁₄ is a cycloalkylene group, the following groups are included: 1,3-cyclohexylene and 1,4-cyclohexylene.

If R ₁₄ is an arylene group, this is in particular the following groups: 1,3-f, nylene or 1,4
A phenylene group.

As a C 2 -C 12 alkylene group, Z is straight-chain or branched. It is, for example, ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,
1-ethylidene group, 2,2-propylidene group, 2,2-
Amylidene group or 2-ethylhexamethylene group.
Alkylene groups having 2 to 6 carbon atoms are preferred.

Z represents 4 carbon atoms interrupted by oxygen
When it is from 1 to 12 alkylene groups, it is for example:
_{-CH 2 -CH 2 -O-CH 2} -CH 2 -, - CH 2 -
CH ₂ —O—CH ₂ —CH ₂ —CH ₂ —, —CH ₂ —C
_{H 2 -O-CH 2 -CH 2} -O-CH 2 -CH 2 - or _{-CH 2 -CH 2 -O-CH 2} -CH 2 -O-CH 2 -
CH ₂ —O—CH ₂ —CH ₂ — and the alkylene group was interrupted by a nitrogen atom, a group —N (R ₁₆ ) —, where R ₁₆ is defined as above. If, for example, _{-CH 2 -CH 2 -NH-CH 2} -CH 2 -CH 2
_{-CH 2 -, - CH 2 -CH} 2 -CH 2 -NH- (CH
_{2) 8} - or _{-CH 2 -CH 2 -CH 2 -N (} CH 3)
—CH ₂ —CH (C ₂ H ₅ ) (CH ₂ ) ₄ —.

As a C 3 -C 12 alkylene group substituted by a hydroxyl group, Z is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in particular, 2-hydroxytrimethylene.

Z as a cyclohexylene group is, for example, a 1,4-cyclohexylene group, especially a 1,2-cyclohexylene group.

Z as a phenylene group is, for example, an m-phenylene group or a p-phenylene group.

M can be 0, 1 or 2, but is preferably 2.

P is preferably 1, but can be 0 if both X and Y are linked by nitrogen.

R ₁ as an alkyl group having 1 to 8 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n -Pentyl group, tert-
Amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. A tert-butyl group is preferred.

R ₁₆ , R ₁₇ and R ₂₀ as C ₁ -C 12 alkyl have the same meanings as given above for R ₁ , and additionally linear or branched nonyl. Group, decyl group, undecyl group or dodecyl group.

When R ₁₆ and R ₁₇ are alkyl groups interrupted by an oxygen atom, the applicable examples are the same as those described in the above sentence for Z.

Examples of R ₁₆ and R ₁₇ as aralkyl groups are: benzyl, α-methylbenzyl, 1-phenylethyl, α, α-dimethylbenzyl or 1-phenylpropyl.

When Z is an ethylene group, R ₁₆ and R ₁₇ together form an ethylene group, which is equivalent to being bridged by a piperazine group.

When Y is a group —N (R ₁₇ ) —, R ₁₅ and R ₁₇ together form the group —CO—CH ＝ CH—CO—, and thus the group —X— (Z) _p -Substituent on

Embedded image To form

However, a preferred meaning of R ₁₅ is-
CO—C (R ₁₈ ) ＣＨCHR ₁₄ , wherein R ₁₈ and R ₁₉ are preferably a methyl group and especially a hydrogen atom.

R ₂ is —CH ₂ —CH ₂ —CO—O—C
(G) = CH ₂ and G represents a hydrogen atom or a methyl group.

The invention also relates to compounds of the formula I, II, III or IV

Embedded image {Wherein, G ₁ represents a hydrogen atom or a halogen atom; G ₂
Is a cyano group, E ₃ SO—, E ₃ SO ₂ —, —COO
_{G 3, CF 3 -, -} P (O) (C 6 H 5) 2, -CO-
G _{3 represents} —CO—NH—G ₃ or —CO—N (G ₃ ) ₂ ; G ₃ is a straight-chain or branched alkyl group having 1 to 24 carbon atoms, and having 2 to 18 carbon atoms. A linear or branched alkenyl group, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, a phenyl group, and a carbon atom having 1 to 4 carbon atoms on a phenyl ring;
Represents the above phenyl group or the above phenylalkyl group substituted with 1 to 4 alkyl groups; and E ₁ represents a hydrogen atom,
E ₂ represents a phenylalkyl group having 7 to 15 carbon atoms, a phenyl group, the phenyl group substituted with 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the phenylalkyl group; 1 or 2 atoms
A straight-chain or branched alkyl group having 4 to 18 carbon atoms; a straight-chain or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 5 to 12 carbon atoms;
A phenylalkyl group, a phenyl group, the above-mentioned phenyl group or the above-mentioned phenylalkyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or E ₂ represents a hydroxyl group or -OE. ₄ (where E
₄ represents a linear or branched alkyl group having 1 to 24 carbon atoms. ); One or more —OH, —OCO-E ₁₁ ,
-OE _4, the alkyl group substituted by -NCO or -NH _2, or mixtures thereof; or one or more -O-,
—NH— or —NE ₄ — or interrupted by a mixture thereof and unsubstituted or one or more —OH, —OE ₄
Or an alkyl group or the alkenyl group of the optionally substituted by -NH ₂ group, or mixtures thereof; or E ₂ is -SE _3, -NHE ₃ or -N (E _{3) 2}
Or E ₂ represents — (CH ₂ ) _m —CO—X— (Z) _p —
Y—E ₁₅ [wherein, X represents —O— or —N (E ₁₆ ) —, Y represents —O— or —N (E ₁₇ ) —, and Z represents an alkylene having 2 to 12 carbon atoms. Represents an alkylene group having 4 to 12 carbon atoms interrupted by a group, 1 to 3 nitrogen atoms, oxygen atoms or a mixture thereof, or an alkylene group having 3 to 12 carbon atoms, butenylene group, butynylene group, Represents a cyclohexylene group or a phenylene group, each of which is substituted by a hydroxyl group, m represents 0, 1 or 2, p represents 1 or X
And Y are —N (E ₁₆ ) — and —N (E ₁₇ ), respectively, and represent 0, and E ₁₅ is a group —CO—C (E ₁₈ ) = C (H) E
Or it represents a _19, Y is -N (E ₁₇₎ - When referring to, E ₁₇
Together with the group —CO—CH ＝ CH—CO—, E ₁₈ represents a hydrogen atom or a methyl group, and E ₁₉ represents a hydrogen atom,
Methyl or _{-CO-X-E 20, E} 20 is hydrogen atom, an alkyl group or the formula of 1 to 12 carbon atoms

Embedded image (Wherein, symbols G ₁ , G ₂ , E ₁ , X, Z, m and p have the same definitions as above), and E ₁₆ and E ₁₇ independently represent a hydrogen atom, a carbon atom number of 1 Represents a C 12 -C 12 alkyl group, a C 3 -C 12 alkyl group interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or a C 7 -C 15 aralkyl group; E _{16 in the} case of representing an ethylene group together with E ₁₇ also forms an ethylene group. ]; N is 1
Or 2 and n represents 1, when E ₅ is Cl, OE
₆ or NE ₇ E ₈ or E ₅ is —PO (O
E ₁₂ ) ₂ , represents —OSi (E ₁₁ ) ₃ or —OCO—E ₁₁ , or is interrupted by —O—, —S— or —NE ₁₁ —, and is unsubstituted or —OH or —OCO— cycloalkyl group 12 C 5 carbon atoms are substituted by unsubstituted or -OH;; alkyl group 24 to be straight or C 1 -C branched optionally substituted by E ₁₁ unsubstituted Or a straight-chain or branched alkenyl group having 2 to 18 carbon atoms, substituted by -OH, an aralkyl group having 7 to 15 carbon atoms, -CH ₂ -C
Represents HOH-E ₁₃ or a glycidyl group; E ₆ represents a hydrogen atom, a straight-chain or branched C 1 -C 24 unsubstituted or substituted by one or more OH, OE ₄ or NH ₂ groups. Represents an alkyl group, or -OE ₆ is-(O
CH ₂ CH _{2) w} OH or _{- (OCH 2 CH 2) w} OE
_{21 wherein} w represents 1 to 12 and E ₂₁ represents an alkyl group having 1 to 12 carbon atoms; E ₇ and E ₈ independently of one another are hydrogen, 1 to 12 carbon atoms. 18 alkyl group; -O -, - S- or -NE ₁₁ - by alkyl group having 3 to carbon atoms and straight-chain or branched interrupted 18, cycloalkyl groups having 5 to 12 carbon atoms, carbon Represents an aryl group having 6 to 14 atoms or a hydroxyalkyl group having 1 to 3 carbon atoms,
Or E ₇ and E ₈ together with an N atom represent a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring; when n represents 2, E ₅ represents a divalent group —O—E ₉ —
O- or _{-N (E 11) -E 10 -N} (E 11) - the one expressed; E ₉ represents an alkylene group, an alkenylene group having 4 to 8 carbon atoms of 8 to 2 carbon atoms, carbon atoms Formula 4 alkynylene group, cyclohexylene group, -O- or -CH
_{2 -CHOH-CH 2 -O-E} 14 -O-CH 2 -CHO
H-CH ₂ - C 4 -C straight or branched chain which is interrupted by represents 10 alkylene, E ₁₀ is a good straight or branched chain optionally interrupted by -O- An alkylene group having 2 to 12 carbon atoms, a cyclohexylene group or

Embedded image Or E ₁₀ and E ₁₁ together with two nitrogen atoms form a piperazine ring, E ₁₄ is a linear or branched C 2 -C 8 alkylene group, —O— A linear or branched alkylene group having 4 to 10 carbon atoms, a cycloalkylene group, an arylene group or

Embedded image And E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or E ₇ and E ₈
Are together an alkylene group having 4 to 6 carbon atoms,
3-oxapentamethylene, 3-imino pentamethylene or 3-methyl imino pentamethylene; E ₁₁
Is a hydrogen atom, a linear or branched C 1 -C 18
An alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, a linear or branched alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an alkyl group having 7 to 15 carbon atoms. E ₁₂ represents a linear or branched alkyl group having 1 to 18 carbon atoms,
A straight-chain or branched-chain alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms or an aralkyl group having 7 to 15 carbon atoms ; E ₁₃ is H, -PO (O
E ₁₂₎ C 1 -C straight or branched chain substituted by ₂ 18 alkyl, phenyl group which is substituted by unsubstituted or OH, C 7 -C 15
Represents aralkyl group or -CH ₂ OE _12; E ₃ is alkyl of 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, C 3 -C 1
An alkenyl group having 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or one or two alkyl groups having 1 to 4 carbon atoms. L represents an alkylene having 1 to 12 carbon atoms, wherein said aryl group or perfluoroalkyl moiety substituted by is a 1,1,2,2-tetrahydroperfluoroalkyl group having 6 to 16 carbon atoms; Group, 2 to 1 carbon atoms
2 represents an alkylidene group, a benzylidene group, a p-xylylene group or a cycloalkylidene group, and T represents -SO
_{-, - SO 2 -, -} SO-E-SO -, - SO 2 -E-
SO _2- , -CO-, -CO-E-CO-, -COO-
E-OCO- or _{-CO-NG 5 -E-NG 5} -CO-
(Wherein E is an alkylene group having 2 to 12 carbon atoms,
A cycloalkylene group having 5 to 12 carbon atoms or an alkylene group interrupted by or terminated by a cyclohexylene group having 8 to 12 carbon atoms,
G ₅ represents G ₃ or a hydrogen atom. ); However, G ₂
There E ₃ SO- or E ₃ SO ₂ - if it is, E ₁ is provided that is not a phenyl group. It also relates to novel benzotriazoles represented by｝.

Preferably, the novel benzotriazoles are of the formula I ′

Embedded image (Wherein G ₂ is a cyano group, E ₃ SO ₂ −, CF ₃ −, −
COO-G ₃ -CO-NHG ₃ or -CO-N (G ₃ ) ₂
G ₃ represents an alkyl group having 1 to 12 carbon atoms; E ₁ represents a hydrogen atom, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or an alkyl group having 1 to 4 carbon atoms on the phenyl ring. phenyl or above which is substituted by one or two groups represents a phenyl alkyl group; E ₂ is alkyl of 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group or a -CH of 7 to 15 carbon atoms ₂ CH ₂ COOG ₄ wherein G ₄ is substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, interrupted by 1 to 6 —O— atoms, or E ₃ represents an alkyl group as defined above, which is substituted and interrupted by 1 to 6 —O— atoms, and E ₃ represents an alkyl group having 8 to 18 carbon atoms, G represents an aryl group having 6 to 10 atoms or the above-mentioned aryl group substituted by one or two alkyl groups having 1 to 4 carbon atoms;
_{When 2} is E ₃ SO— or E ₃ SO ₂ —, E ₁ is not a phenylalkyl group. Is a compound represented by

Most preferably, in formula I ′, G ₂ is a cyano group, E ₃ SO ₂ —, CF ₃ —, —COO-G ₃ or —C
G represents an ON (G ₃ ) ₂ ; G ₃ represents an alkyl group having 1 to 8 carbon atoms; E ₁ represents a hydrogen atom, a phenyl group or α.
- represents cumyl group; E ₂ represents an alkyl group of 12 C 4 -C, and E ₃ represents a phenyl group or octyl group, and provided that, G ₂ is E ₃ SO ₂ - If an E ₁ Is not an α-cumyl group.

It is particularly preferred that in formula I ', G ₂ is CF
_A compound wherein E ₁ represents an α-cumyl group or a phenyl group, and E ₂ represents a tert-butyl group or a tert-octyl group.

The present invention also relates to (a) an organic material which undergoes thermal, oxidative or photo-induced decomposition, and
Or a composition stabilized against heat, oxidation or light induced degradation comprising an effective stabilizing amount of the compound represented by

Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, especially a thermoplastic polymer.

Most preferably, the polymer is a polyolefin or polycarbonate, especially polyethylene or polypropylene; most especially polypropylene.

In another preferred embodiment of the present invention, the organic material is a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin having a carbamate side group crosslinked with melamine or a carbamate group. And a resin selected from the group consisting of acrylamine resins crosslinked with melamine.

[0055] Most preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.

Still, in another preferred embodiment of the invention, the organic material is a recording material.

The recording material of the present invention comprises a pressure-sensitive copying system,
Suitable for photocopying systems, thermal copying systems, photographic materials and inkjet printing using microcapsules.

The recording materials according to the invention are distinguished by an unexpected improvement in quality, in particular with regard to the fastness to light.

The recording material according to the invention has a structure which is known for a special use. They consist of conventional carriers, for example paper or plastic films, which are covered by one or more layers. Depending on the type of material, these layers contain the appropriate necessary ingredients, for example in the case of photographic materials silver halide emulsions, dye couplers, dyes and the like. Particularly suitable materials for ink jet printing have a layer on a conventional carrier which is particularly absorbent for the ink. In this case, the paper simultaneously functions as a carrier material and an ink absorbing layer. Suitable materials for ink jet printing are described, for example, in US Pat. 5,073,448 (incorporated herein by reference).

The recording material is, for example, a projection film (pr
object film), it can also be transparent.

The compounds of the formulas I, II, III or IV are incorporated into the carder material simultaneously with the production of the carding material, for example by being added to the paper pulp in the production of paper. be able to.
Another method of application is to spray the carding material with an aqueous solution of a compound represented by Formula I, II, III or IV, or to add the compound to a coating composition.

Coating compositions intended for transparent recording materials suitable for transparent films must not contain light-dispersing particles such as pigments or fillers.

Dye-binding coating compositions may contain a number of other additives, such as antioxidants, light stabilizers (including UV absorbers not belonging to the UV absorbers of the present invention), viscosity improvers. , An optical brightener, a biocide and / or an antistatic agent.

The coating compositions are usually prepared as follows: water-soluble components, such as binders, are dissolved in water and stirred together. Solid components, such as the above-mentioned fillers and other additives, are suspended in this aqueous medium. The dispersion is performed by, for example, an ultrasonic sample device, a turbine stirrer, a homogenizer, a colloid mill, a bead mill, a sand mill, a high-speed stirrer, or the like. The compounds of formulas I, II, III and IV can be easily incorporated into coating compositions.

[0065] recording material of the present invention, preferably, 1 to 5000 mg / m ^2, in particular 50-1200mg / m ²
Containing a compound of formula I

As already mentioned, the recording materials according to the invention cover a wide range of fields. The compounds of the formulas I, II, III and IV can be used, for example, in pressure-sensitive copying systems. They are introduced to protect the microencapsulated dye precursors present therein from light in the paper, or to protect the dyes formed therein from light into the binder of the developing layer. .

A photocopying system using photosensitive microcapsules developed by pressure is disclosed in US Pat.
4,416,966; 4,483,912; 4,35
2,200; 4,535,050; 4,536,46
3, 4,551,407; 4,562,137 and 4,
608,330, and also EP-A-139,479;
EP-A-162,664; EP-A-164,931;
EP-A-237,024; EP-A-237,025
And EP-A-260,129. In all these systems, the compounds of the present invention may be incorporated into the dye receiving layer. Merrill compounds, however, may be included in the donor layer to protect the color former from light.

Photographic materials which can be stabilized are layers containing photographic dyes and such dyes or their precursors, for example photographic papers and films. Suitable materials are described, for example, in US Pat. No. 5,364,749 (herein incorporated by reference). Formula I, II, III or IV
Here functions as an ultraviolet filter against electrostatic flashes. In color photographic materials, couplers and dyes are protected against photochemical degradation.

The compounds of the present invention can be used for all types of color photographic materials. For example, they can be used for color photographic paper, color reversal photographic paper, direct positive color materials, color negative films, color positive films, color reversal films and the like. They are preferably, in particular, reversal substrates or form po
It is preferably used for photographic color materials, including active materials.

The color photographic recording material usually comprises, on a support, a blue-sensitive and / or green-sensitive and / or red-sensitive silver halide emulsion layer and, if desired, a protective layer.
Preferably, it is present in the above-mentioned green / red-sensitive silver halide emulsion layer, in the above-mentioned layer between the green- and red-sensitive layers, or in the layer above the silver halide emulsion layer.

The compounds represented by the formulas I, II, III or IV can be used in recording materials based on the principle of photopolymerization, photoplasticization or microcapsule splitting, or with heat- and light-sensitive diazonium salts, oxidizing agents. It may also be used when a white or leuco dye having a dye or a lactone having a Lewis acid is used.

Furthermore, they are useful for dye diffusion transfer (die diffusion transfer) printing, hot wax transfer printing and non-matrix printing and electrostatically.
It can be used for use in electrographs, electrophoresis, magnetographs and laser electrograph printers and pen-plotters. Among the above, the recording material for dye diffusion transfer printing is preferably that recorded in, for example, EP-A-507,734.

They may be used in inks, preferably for ink jet printing, for example in US Pat. 5,09
8,477 (which is hereby incorporated by reference).

The compounds of the present invention exhibit excellent hydrolytic stability, handling and storage stability and excellent resistance to extractability when present in a stabilized composition.

The process for preparing the compounds of the present invention comprises:
It is described in the prior art. The intermediates required to prepare the compounds of the present invention are mostly commercial products.

Among these, particularly preferred compounds are X and Y
Is -O-; and especially compounds wherein X and Y are both -O-.

In general, the polymers that can be stabilized include the following polymers: Mono- and di-olefin polymers such as polypropylene, polyisobutylene, polybutene
1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as cycloolefins such as cyclopentene or norbornene, polyethylene (which can be cross-linked if desired), such as high density polyethylene (HDPE), high density polyethylene (HDP)
E), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, ie polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various methods, and in particular by the following methods: a) Radical polymerization (usually under high pressure and high temperature) B) catalytic polymerization using a catalyst containing one or more metals of groups IVb, Vb, VIb or VIII of the periodic table. These metals usually have one or more ligands, which may be π- or σ-coordinated, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. These metal complexes may be in free form or fixed on a support, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used as such during the polymerization or it may be another activator, typically an alkyl metal, metal hydride, alkyl metal halide, alkyl metal oxide or alkyl metal oxane (these metals may be of the Periodic Table). Ia, II
a and / or IIIa. ). The activator may be advantageously modified with another ester, ether, amine or silyl ether group. These catalyst systems are usually Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC).
Called.

2. A mixture of the polymers described in 1),
For example, a mixture of polypropylene and polyisobutylene,
A mixture of polypropylene and polyethylene (eg, PP
/ HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg, LDPE / HDPE).

3. Copolymers of monoolefins with diolefins or with other vinyl monomers, such as ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its low density polyethylene (LDP)
E), propylene-isobutylene copolymer, propylene-butene-1 copolymer, ethylene-
Butene-1 copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, propylene-butadiene copolymer, isobutylene-isoprene copolymer, ethylene-alkyl acrylate copolymer, Ethylene-alkyl methacrylate copolymer, ethylene-vinyl acetate
Copolymers and their copolymers with carbon monoxide or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; As well as mixtures of such copolymers and their mixtures with the polymers described under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE
/ Ethylene-acrylic acid-copolymer (EAA), LL
DPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.

4. Hydrocarbon resins (eg C ₅ -C ₉ ) and their hydrogenated modifications (eg tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene-maleic anhydride,
Styrene-acrylonitrile-methyl acrylate; a high-impact mixture of a styrene copolymer and another polymer, such as a polyacrylate, diene polymer or ethylene-propylene-diene terpolymer; and a block copolymer of styrene, such as styrene-butadiene-styrene, styrene- Isoprene-styrene, styrene-ethylene-butylene-styrene or styrene-ethylene-propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as styrene, polybutadiene-styrene or polybutadiene-
Styrene to acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; styrene, acrylonitrile and methyl methacrylate to polybutadiene; styrene and maleic anhydride to polybutadiene; styrene to polybutadiene; styrene to acrylonitrile and maleic anhydride or maleimide; polybutadiene to styrene. Styrene and alkyl acrylate or alkyl methacrylate on polybutadiene; styrene and acrylonitrile on ethylene-propylene-diene terpolymer; styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate; styrene and acrylonitrile on acrylate / butadiene copolymer. , And mixtures of the copolymers listed in these and 6), for example ABS-, MBS-, A
A copolymer mixture known as SA- or AES-polymer.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymer of ethylene and chlorinated ethylene, epichlorohydrin homo-
And copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride,
Polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymer.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned in the above item 9) with each other or with other unsaturated monomers, such as acrylonitrile-butadiene copolymer, acrylonitrile-alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide. Copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or their acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;
And copolymers thereof with the olefins described in 1) above.

12. Like polyalkylene glycols,
Homopolymers and copolymers of cyclic ethers, such as polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.

13. Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyether-containing polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Diamines and dicarboxylic acids and / or
Or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams. For example, polyamide 4, polyamide 6, polyamide 6/6, 6/10,
6/9, 6/12, 4/6, 12/12, polyamide 1
1, polyamide 12, aromatic polyamides starting from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally an elastomer as modifier, such as poly (2, 4,4-trimethylhexamethylene) terephthalamide or poly-m
-Phenylene isophthalamide. Graft copolymers of the polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or graft copolymers of the polyamides with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, polyamides or copolyamides modified with EPDM or ABS. Polyamide condensed during processing (RIM-polyamide system).

17. Polyurea, polyimide, polyamide
Imides and polybenzimidazoles.

18. Dicarboxylic acids and diols and / or
Or polyesters derived from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4
Block copolyetheresters derived from dimethylol-cyclohexane terephthalate and polyhydroxybenzoate, and polyethers containing hydroxy end groups; and polycarbonate or MB
Also polyester modified with S.

19. Polycarbonates and polyester-carbonates.

20. Polysulfone, polyether sulfone and polyether ketone.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Dry and non-dry alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and of vinyl compounds as crosslinkers and their halogen-containing modified products with low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins or acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxy, for example from bisglycidyl ether or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, natural rubber, gelatin and chemically modified derivatives thereof such as cellulose acetate, cellulose propionate and cellulose butyrate, or such as cellulose ethers such as methylcellulose And rosin and derivatives thereof.

28. Mixtures of the aforementioned polymers (polyblends), for example PP / EPDM, polyamide / EPDM
Or ABS, PVC / EVA, PVC / ABS, PV
C / MBS, PC / ABS, PBTP / ABS, PC /
ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic P
UR, POM / acrylate, POM / MBS, PPO
/ HIPS, PPO / PA6.6 and copolymer, P
A / HDPE, PA / PP, PA / PPO.

29. Pure monomeric compounds or natural and synthetic organic materials composed of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or synthetic esters (
Mixtures of the above oils, fats and waxes based on, for example, phthalate, adipate, phosphate or trimellitate) and mineral oils mixed in suitable weight ratios of synthetic esters, the materials being as fiber spinning oils for polymers and It can be used as an aqueous emulsion of such a material.

30. Aqueous emulsions of natural or synthetic rubbers, such as natural latex or carboxylated styrene / butadiene copolymer latex.

31. For example, US Pat. 4,259,4
67, a soft hydrophilic polysiloxane as described in US Pat. Polysiloxanes such as the hard polyorganosiloxanes described in 4,355,147.

32. Polyketimine which is blended with unsaturated acrylic polyacetoacetate resin or unsaturated acrylic resin. Unsaturated acrylic resin is urethane acrylate,
Includes polyether acrylates, vinyl or acrylic copolymers with pendant unsaturated groups, and acrylate melamine. Polyketimines are synthesized from polyamines and ketones in the presence of an acid catalyst.

33. A radiation-curable composition comprising an ethylenically unsaturated monomer or oligomer and an unsaturated aliphatic oligomer.

34. An epoxy melamine resin such as a light stable epoxy resin crosslinked by a co-etherified high solid melamine resin with an epoxy function such as LSE 4103.

In general, the compounds of the present invention will be used in amounts of about 0.01 to about 5% by weight of the composition to be stabilized, but will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 3%, and especially about 0.05
Or about 1%.

The stabilizers of the present invention can be easily incorporated into organic polymers by conventional techniques at a convenient stage prior to the manufacture of molded articles therefrom. For example, the stabilizer may be mixed with the polymer in the form of a dry powder, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer. The resulting stabilized polymer composition of the present invention may optionally contain from about 0.01 to about 5% by weight, preferably about 0.0
It may also contain various conventional additives in amounts of from 25 to about 2% by weight and in particular from about 0.1 to 1% by weight, such as the substances listed below or mixtures thereof.

[0114] 1. Antioxidants 1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, 2,6-di-tert-butyl-4-n-
Butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6
-Dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.

1.2. Alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl
Ethers such as 2,2'-thiobis (6-tert-butyl-4
-Methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-
Methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol).

1.4. Alkylidene bisphenol,
For example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-
Methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,2 '-Methylenebis [6-
(Α-methylbenzyl) -4-nonylphenol], 2,
2'-methylenebis [6- (α, α-dimethylbenzyl)
-4-nonylphenol], 2,2'-methylenebis (4,6
-Di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4 '-Methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-
(Hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl- 4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2)
-Methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], di (3
-Tert-butyl-4-hydroxy-5-methylphenyl)
Dicyclopentadiene, bis [2- (3'-tert-butyl-
2'-Hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

1.5. Benzyl compounds, for example 1,3,5
-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis (3,5-di-
Tert-butyl-4-hydroxybenzyl) sulfide, 3,
5-Di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester bis (4-tert-butyl-3
-Hydroxy-2,6-dimethylbenzyl) dithioterephthalate, 1,3,5-tris (3,5-di-tert-butyl-4-
Hydroxybenzyl isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4
-Dioctadecyl hydroxybenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

1.6. Acylaminophenol, for example
If lauric acid 4-hydroxyanilide, stearic acid 4
-Hydroxyanilide, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, octyl N- (3,5-di-
Tert-butyl-4-hydroxyphenyl) -carbamate.

1.7. β- (3,5-ditert-butyl-4
-Hydroxyphenyl) propionic acid
Is an ester with a polyhydric alcohol , examples of alcohols: methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris (hydroxyethyl) isocyanurate, thiodiethylene glycol, N , N'-Bis (hydroxyethyl) oxalic acid diamide, triethanolamine, triisopropylethanolamine.

1.8. β- (5-tert-butyl-4-h
(Droxy-3-methylphenyl) propionic acid
Esters with monohydric or polyhydric alcohols , examples of alcohols: methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol,
Tris (hydroxyethyl) isocyanurate, thiodiethylene glycol, N, N'-bis (hydroxyethyl)
Oxalic acid diamide, triethanolamine, triisopropylethanolamine.

1.9 β- (3,5-di-tert-butyl-4-
Amides of (hydroxyphenyl) propionic acid such as N,
N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene Diamine, N, N'-bis (3,5
-Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

1.10. Diarylamines such as diphenylamine , N-phenyl-1-naphthylamine,
N- (4-tert-octylphenyl) -1-naphthylamine, 4,4′-di-tert-octyl-diphenylamine, N-phenylbenzylamine and 2,4,4
A reaction product of trimethylpentene, a reaction product of diphenylamine and 2,4,4-trimethylpentene,
Reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

[0124] 2. UV absorbers and light stabilizers 2.1. 2- (2'-hydroxyphenyl) benzotri
Azole , for example, 5'-methyl, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5- Chloro-3 ', 5'-di-tert-butyl-,
5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3 ', 5'-
Di-tert-amyl and 3 ', 5'-bis (α, α-dimethylbenzyl) derivative, 3'-tert-butyl-5'-(2-
(Omega-hydroxy-octa- (ethyleneoxy) carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5 '-(2-octyloxycarbonyl) ethyl-, and Dodecylated-5'-methyl-derivatives.

2.2. 2-hydroxy-benzopheno
Emissions, such as 4-hydroxy -, 4-methoxy -, 4-octoxy -, 4-decyloxy -, 4-dodecyloxy -, 4-benzyloxy -, 4,2 ', 4'-trihydroxy - and 2'Hydroxy-4,4'-dimethoxy derivative.

2.3. Substituted and unsubstituted benzoic
Esters of acids such as phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl
Salicylate, dibenzoylresorcinol, bis (4
-Tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, and 3,5-di-tert-butyl-4 -Hexadecyl hydroxybenzoate.

2.4. Acrylates such as α-cyano-β, β-diphenyl-acrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl Esters, α-carbomethoxy-p-methoxycinnamic acid methyl ester, and N- (β-carbomethoxy-β-cyanovinyl) -2
-Methylindoline.

2.5. Nickel compounds , such as 2,2'-
Nickel complexes of thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], such as 1: 1 or 1: 2 complexes, optionally n-butylamine, triethanolamine or N- With other ligands such as cyclohexyl-diethanolamine, nickel dibutyl dithiocarbamate, monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, e.g. nickel salt of methyl or ethyl ester, 2- Nickel complexes of ketoxime, such as hydroxy-4-methyl-phenylundecylketoxime, 1-phenyl-4-
Nickel complexes of lauroyl-5-hydroxypyrazole, optionally with other ligands.

2.6 Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n
-Butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, 1- (2-hydroxyethyl) -2,2, 6,
Condensation product of 6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino A condensation product with -2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4
-Piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-
Butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), bis (1-octyloxy-2,2,6,6- Tetramethylpiperidin-4-yl) sebacate.

2.7 Oxalic acid diamides , for example 4,4′-
Di-octyl-oxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide, 2,2 '
-Di-dodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-
Bis (3-dimethylaminopropyl) oxanilide, 2-
Ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures of this compound with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide and ortho- and para-methoxy Mixtures of disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl)
L) -s-triazine , for example, 2,6-bis (2,4-
Dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl]-
6- (4-chlorophenyl) -s-triazine; 2,4
-Bis [2-hydroxy-4- (2-hydroxy-4-
(2-hydroxyethoxy) phenyl] -6- (2,4
-Dimethylphenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy)-
Phenyl] -6- (4-bromophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine; 2 , 4-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl)
-S-triazine;

[0132] 3. Metal deactivators such as N, N'-diphenyloxalic acid diamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 -Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalodihydrazide [bis (benzylidene) oxalodi
hydrazide].

[0133] 4. Phosphites and phosphonites ,
For example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butyl) Phenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl-phenyl) pentaerythritol diphosphite , Screws (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite.

[0134] 5. Compounds that decompose peroxides , such as esters of β-thiodipropionic acid, such as lauryl,
Stearyl, myristyl or tridecyl esters; zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

[0135] 6. Hydroxylamine , such as N, N-
Dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-
From ditetradecyl hydroxylamine, N, N-dihexadecyl hydroxylamine, N, N-dioctadecyl hydroxylamine, N-hexadecyl-N-octadecyl hydroxylamine, N-heptadecyl-N-octadecyl hydroxylamine, hydrogenated tallow amine Derived N, N-dialkylhydroxylamine.

[0136] 7. Nitrones such as N-benzyl-α
-Phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-
Tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N
Heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, nitrones derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow.

[0137] 8. Polyamide stabilizers , for example copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

[0138] 9. Basic co-stabilizers , such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, such as Ca stearate, Zn Stearate, Mg stearate, Na ricinolate and K palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.

[0139] 10. Nucleating agents such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

[0140] 11. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

[0141] 12. Other additives , such as plasticizers,
Lubricants, emulsifiers, pigments, brighteners, flame retardants, antistatic agents,
Blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

13. Benzofuranones and indolinones
Kind, for example, US-A-4325863, US- A-43
38-244, or 3- [4-
(2-acetoxyethoxy) phenyl] -5,7-di-
tert-butyl-benzofuran-2-one, 5,7-
Di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one;
3,3'-bis [5,7-di-tert-butyl-3-
(4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3
-(4-ethoxyphenyl) benzofuran-2-one,
3- (4-acetoxy-3,5-dimethylphenyl)-
5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.

13. The co-stabilizers other than the benzofuranones mentioned in the above are added, for example, at a concentration of 0.01 to 10%, based on the total weight of the material to be stabilized.

Further preferred compositions contain, in addition to components (a) and (b), in particular phenolic antioxidants, light stabilizers or processing stabilizers.

Particularly preferred additives are the above-mentioned phenolic antioxidants (item 1. above), sterically hindered amines (item 2.6 above), phosphites and phosphonites (item 4 above). ) And compounds that decompose peroxides (item 5. above).

Further additives (stabilizers) which are also particularly preferred are, for example, US-A-4,325,863, US-A.
A-4,338,244 or US-A-5,175,3
Benzofuran-2-one as described in No. 12.

Particularly interesting phenolic antioxidants are:
n-octadecyl 3,5-di-tert-butyl-4
-Hydroxyhydrocinnamate, neopentanetetrayltetrakis (3,5-di-tert-butyl-4-)
Hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, thiodiethylene bis (3,5-di-te
rt-butyl-4-hydroxyhydrocinnamate),
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-
Methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-
Cresol, 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1,3,5-tris [2-
(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate,
3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3 , 5-Di-tert-butyl-4-hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-
Bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (ethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis [3,3-di (3-
tert-butyl-4-hydroxyphenyl) butyrate], octyl 3,5-di-tert-butyl-4-
Hydroxybenzylmercaptoacetate, bis (3
5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,
5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) -ethyl] -oxamide.

The most preferred phenolic antioxidant is neopentanetetrayl tetrakis (3,5-di-te
rt-butyl-4-hydroxyhydrocinnamate),
n-octadecyl 3,5-di-tert-butyl-4
-Hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5
-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-ter
t-butyl-p-cresol or 2,2′-ethylidene-bis (4,6-di-tert-butylphenol).

The sterically hindered amines of particular interest are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl). Il) sebacate, di (1,2,
2,6,6-pentamethylpiperidin-4-yl)
(3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl-2,2,
6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n
-Octyl-7,7,9,9-tetramethyl-1,3,
8-triazaspiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethyl-4-piperidin-4-yl) nitrilotriacetate, 1,2
-Bis (2,2,4,4-tetramethyl-3-oxopiperazin-4-yl) ethane, 2,2,6,6-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [ 5.1.11.2] Hen Eikosan, 2, 4
-Dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,
Polycondensation product with 2,6,6-tetramethylpiperidine), 1- (2-hydroxyethyl) -2,2,6,6-
Polycondensation product of tetramethyl-4-hydroxypiperidine and succinic acid, 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 1,
Polycondensation product with 2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2, 6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, 2,4-dichloro-6-morpholino-s-triazine and 4,4′-hexamethylenebis (amino- Polycondensation product with 2,2,6,6-tetramethylpiperidine), N, N ′, N ″, N ″ ′-tetrakis [(4,6-bis (butyl-1,2,2,6, 6-pentamethylpiperidin-4-yl) -amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidine-4. -Il / β, β, β ', β' -Tetramethyl-3,9,-(2,4,8,10-tetraoxaspiro [5.5] -undecane) diethyl] 1,2,3
4-butanetetracarboxylate, mixed [1,
2,2,6,6-pentamethylpiperidin-4-yl /
β, β, β ′, β′-tetramethyl-3,9- (2,
4,8,10-tetraoxaspiro [5.5] -undecane) diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis (2,2,6,6
-Tetramethylpiperidine-4-carboxylate),
4,4'-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecylsuccinic acid Imide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N
-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-
1,3,8-Triazaspiro [4.5] decane-2,4
-Dione, di- (1-octyloxy-2,2,6,6
-Tetramethylpiperidin-4-yl) sebacate,
Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1
-Octyloxy-2,2,6,6-tetramethyl-4
-Hydroxy-piperidine, poly-{[6-tert-
Octylamino-s-triazine-2,4-diyl]
[2- (1-cyclohexyloxy-2,2,6,6-
Tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,
6,6-tetramethylpiperidin-4-yl) imino]
And 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-
Yl) -n-butylamino] -s-triazine.

The most preferred sterically hindered amines are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) Sebacate, Di (1, 2,
2,6,6-pentamethylpiperidin-4-yl)
(3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid The condensation products, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylenebis (amino-2,2,
Polycondensation products with (6,6-tetramethylpiperidine)
N, N ', N ", N"'-tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethylpiperidin-4-yl) -amino-s-triazine-2- Il]
-1,10-diamino-4,7-diazadecane, di-
(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-
Piperidine, poly-{[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino- Hexamethylene- [4-
(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] or 2,4,6
-Tris [N- (1-cyclohexyloxy-2,2,
6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

The composition of the present invention may further contain another ultraviolet absorbent selected from the group consisting of s-triazines, oxalic anilides, hydroxybenzophenones, benzoates and α-cyanoacrylates. Can be.

In particular, the composition of the present invention comprises at least one other 2-hydroxyphenyl-2H-benzotriazole; another trisaryl-s-triazine;
Alternatively, it may additionally contain an effective stabilizing amount of a sterically hindered amine or a mixture thereof.

Preferably, 2-hydroxyphenyl-2
H-benzotriazole is 2- (2-hydroxy-3,
5- [di-tert-amylphenyl) -2H-benzotriazole; 2- [2-hydroxy-3,5-di (α,
α-dimethylbenzyl) phenyl] -2H-benzotriazole; 2- [2-hydroxy-3- (α, α-dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole; 2- {2-hydroxy-3 -Tert
-Butyl-5- [2- (omega-hydroxy-octa (ethyleneoxy) carbonyl) ethyl] phenyl}-
2H-benzotriazole; and 2- {2-hydroxy-3-tert-butyl-5- [2- (octyloxy) carbonyl) ethyl] phenyl} -2Hbenzotriazole.

Preferably, other tris-aryl-s-
Triazine is 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,4-diphenyl-6
(2-hydroxy-4-hexyloxyphenyl) -s
-Triazine; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do- / tri-
Decyloxy-2-hydroxypropoxy) phenyl]
-S-triazine and 2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino ] -S-triazine.

The alkyd resin lacquers which can be stabilized against the action of light and moisture according to the invention are the customary stoving lacquers (automobile finishing lacquers) which are used in particular for coating automobiles, such as alkyd / melamine and alkyd / melamine. Lacquer based on acrylic / melamine resin (see H. Wagner and HF Sta)
rx, “Lackkunstharrz” (1977),
99-123). Another crosslinking agent is glycouril (gly
curil) resin, blocked isocyanate or epoxy resin.

The lacquers stabilized according to the invention are:
Metal finish application and solid shade (solid sh
Suitable for both ade) finishing, especially in the case of retouch finishing, as well as for various coil coating applications.
The lacquers stabilized according to the invention are preferably applied according to the customary methods, either by the one-coat method or by the two-coat method. In the latter two-coat method, a primer-containing subbing layer is first applied and then a clear lacquer coating is applied thereon.

The compounds of the present invention may be acid-free catalyzed thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicone, isocyanate or isocyanurate. It should also be noted that this can be applied at Epoxy and epoxy-polyester resins are
Crosslinking is carried out with a conventional crosslinking agent such as an acid, acid anhydride and amine.
Thus, epoxides can be utilized as crosslinkers for various acrylic or polyester resins that have been modified by the presence of reactive groups on the backbone.

When used in a two coat layer finish, the compounds of the present invention can be applied to the clear layer or to both the clear layer and the content pigment subbing layer.

When a water-soluble, water-miscible or water-dispersible coating is desired, an ammonium salt of the acid group present in the resin is formed. Powder coating compositions can be prepared by reacting glycidyl methacrylate with a selected alcohol component.

The benzotriazoles of the present invention are produced by a conventional method for producing such a compound. Conventional methods include diazotization of substituted o-nitroanilines followed by coupling of the resulting diazonium salt with a substituted phenol and reduction of the resulting azobenzene intermediate to the corresponding desired benzotriazole. The starting materials for these benzotriazoles are commercially available multi-items or can be prepared by conventional methods of organic synthesis.

Although the benzotriazoles of the present invention having enhanced durability are particularly suitable for automotive applications, the enhanced durability is not a problem with solar films.
m) It should be taken into account that it may be particularly useful in other applications as required, for example.

[0162]

The following examples are for illustrative purposes only. Example 1 5-trifluoromethyl-2- (2-hydroxy-3-
α-cumyl-5-tert-octylphenyl) -2H
A ) Diazotization of 4-amino-3-nitro-benzotriazole In a 500 ml three-necked flask equipped with a mechanical stirrer,
1.2 g of 4-amino-3-nitro-benzotrifluoride, 52 ml of concentrated hydrochloric acid and 100 ml of distilled water were added. The stirred solution was cooled to 5 ° C. and 17.3 g of sodium nitrite dissolved in 50 ml of water was added.
The solution is stirred at 0-5 ° C for 2 hours, then filtered and stored at -10 ° C.

B) Monoazo adduct In a 1000 ml flask fitted with a mechanical stirrer,
40 g of sodium hydroxide dissolved in ml of methanol and 32.4 g of 2-α-cumyl-4-tert-octylphenol in 50 ml of xylene are added. The solution is cooled to 5 ° C. and the 4-amino-nitro-
The benzotrifluoride diazo solution is added over 2 hours at 0-5 ° C. Then 100 ml of xylene are added and the organic layer is washed with water, aqueous hydrochloric acid, water, aqueous sodium bicarbonate solution and finally with water. The solvent is removed under reduced pressure and the residue is chromatographed (silica gel, heptane;
Purification by ethyl acetate = 95: 5) gives 42.1 g of the addition product as a dark red paste.

C) Reduction of monoazo adduct 20 g of sodium hydroxide,
Charge 0 ml of water, 42.1 g of the monoazo adduct prepared in b) and 400 ml of ethanol. Mix 8
Heat to 0 ° C. and add 27 g of formamidine sulfinic acid in portions with stirring. After 1.5 hours, the solution is cooled to room temperature and 100 ml of water are added. The pH is adjusted to pH 7 with concentrated hydrochloric acid. Ethanol is distilled off under reduced pressure, and the aqueous layer is extracted with methylene chloride. The solvent is then evaporated in vacuo and the residue is chromatographed (silica gel,
Purification by heptane: toluene = 9: 1) and crystallization from ethanol. The title compound is obtained in a yield of 5.6 g as a pale yellow solid melting at 119-121 ° C.

Example 2 5-Fluoro-2- (2-hydroxy-3-α-cumyl
-5-tert-octylphenyl) -2H-benzoto
The title compound was prepared according to the general procedure of Example 1 to give 3
Produced using 1.2 g of 4-fluoro-2-nitroaniline. In part c), an additional 9 g of formamidinesulfinic acid is required to complete the reduction. Purification of the crude product on silica gel (heptane: toluene = 1: 1) gave 4.5 as an off-white solid
g of the title compound are obtained. Subsequent purification by recrystallization from acetonitrile: toluene yielded 1.1 g of 93-96.
This gives the title compound which melts at 0 ° C.

Example 3 5-chloro-2- (2-hydroxy-3-α-cumyl-
5-tert-octylphenyl) -2H-benzotri
Preparation of azoles Performing part a) b) of the general method of Example 1 gives 3
The monoazo intermediate of the title compound is prepared from 39.3 g of 4-chloro-2-nitroaniline. The crude product is purified by recrystallization from methanol to give 70.9 g of a deep red monoazo intermediate.

C) Reduction of the monoazo adduct A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol is heated to 95 ° C. 60.1 g of the above monoazo adduct in 90 g of 2-butanol and 1.3 g
Of a solution of 2,3-dichloro-1,4-naphthoquinone in
Add over 90 minutes with stirring. The reaction mixture was heated to add additional 2- to replace the distillate.
The 2-butanone by-product is removed along with butanol. The reaction mixture is cooled to 85 ° C., washed with 2.5N sulfuric acid and brine, and then concentrated. The residue was recrystallized from methanol: xylene to give 45.6 g of the title compound as 104-1.
Obtained as a pale yellow solid melting at 05 ° C.

Example 4 5-phenylthio-2- (2-hydroxy-3-α-octane
Mill-5-tert-octylphenyl) -2H-ben
Preparation of zotriazole 75 g of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole heated to 90 ° C. and 105 g of N-
To a stirring mixture of methylpyrrolidone, add 4
4.3 g of a 45% aqueous potassium hydroxide solution are added over 15 minutes, then 20.4 g of thiophenol are added over a further 15 minutes. The reaction mixture is then
Heat to −175 ° C. for 4 hours while removing water by distillation. After cooling to 100 ° C., xylene and water are added and the resulting mixture is acidified with a 15% aqueous hydrochloric acid solution.
The organic layer is separated, washed with water and concentrated. The crude product residue is recrystallized from methanol to give 82 g of the title compound as a pale yellow solid melting at 124-125 ° C.

Example 5 5-benzenesulfonyl-2- (2-hydroxy-3-
α-cumyl-5-tert-octylphenyl) -2H
Preparation of benzotriazole In a 1000 mL flask, the 7 prepared in Example 4,
5.2 g of 5-phenylthio-2- (2-hydroxy-
3-α-cumyl-5-tert-octylphenyl)-
2H-benzotriazole, 102 g xylene, 0.1 g
9 g of sodium tungstate dihydrate and 18.4
g of formic acid. Heat the mixture to 50 ° C. To this stirred mixture is slowly added 36.3 g of 50% hydrogen peroxide such that the temperature does not exceed 85 ° C. , Then add additional water and xylene. Separate the organic layer,
Wash with aqueous sodium sulfite, then twice with water and concentrate. The crude product residue was recrystallized from methanol to give 75.2 g of the title compound, 170-17.
Obtained as a pale yellow solid melting at 1 ° C.

Example 6 5-nonylthio-2- (2-hydroxy-3-α-cumy
5-tert-octylphenyl) -2H-benzo
30 g of triazole 5-chloro-2- (2-hydroxy-3-α-
The method of Example 4 is performed using cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17.6 g of nonylmercaptan to produce the title compound.

Example 7 5-nonylsulfonyl-2- (2-hydroxy-3-α
-Cumyl-5-tert-octylphenyl) -2H-
Benzotriazole 5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H -benzotriazole , prepared in Example 6, was purified without purification of the thio intermediate. Using 8.7 g of formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50% hydrogen peroxide to oxidize to sulfone, as a yellow resin showing molecular ion of m / e 631 This gives the title compound.

Example 8 5-chloro-2- (2-hydroxy-3-phenyl-5
-Tert-octylphenyl) -2H-benzotria
Preparation of the sol By carrying out parts a) and b) of the general method of Example 1
Chloro-2-nitroaniline and 2-phenyl-4-te
The monoazo intermediate for the title compound is prepared from rt-octylphenol. The crude product is purified by recrystallization from methanol to give a deep red monoazo adduct.

The title compound was obtained according to the reduction method of Example 3 and 65 g of the monoazo adduct prepared above.
Prepared from 9 g sodium hydroxide and 2.4 g 2,3-dichloro-1,4-naphthoquinone. The crude product is purified on silica gel (hexane: ethyl acetate = 5: 1) to obtain a fraction mainly composed of the title compound exhibiting a molecular ion of m / e433.

Example 9 5-phenylthio-2- (2-hydroxy-3- phenyl
5-tert-octylphenyl) -2H-benzo
Preparation of the triazole The title compound was prepared according to the method of Example 4, 20 g of the compound of Example 8, 20.4 g of a 45% aqueous potassium hydroxide solution, 10.3 g of thiophenol and 100 g of N-
Manufactured from methylpyrrolidone. The title compound is an oil which has been purified by chromatography on silica gel using toluene as eluent.

Example 10 5-Benzenesulfonyl-2- (2-hydroxy-3
-Phenyl-5-tert-octylphenyl) -2H
Preparation of benzotriazole The title compound was prepared according to the method of Example 5, 20 g of the thio compound of Example 9, 6.4 g of formic acid, 15.0 g of 5
Produced from 0% hydrogen peroxide and 0.6 g sodium tungstate dihydrate. Recrystallize 2.5 g of crude material from xylene / methanol to 204-206 ° C.
To give 2.0 g of the purified title compound as a pale yellow powder, which melts.

Example 11 5-chloro-2- (2-hydroxy-3,5-dialkyl
Ruphenyl) -2H-benzotriazole (alkyl group
C _4, C _8, C ₁₂ and C is a) a manufacturing 65.4 g ₁₆ 5-Chloro-2- (2-hydroxy-3 independently,
5-Dialkylphenyl) -2H-benzotriazole, 45 mL dodecene and 13 mL methanesulfonic acid are heated to 170 ° C. under nitrogen. An additional 135 mL of dodecene is added over 4.5 hours. Add 10 reaction mixtures
Cool to 0 ° C. then quench with 400 g of crushed ice and extract three times with ethyl acetate. Combine the organic layers and wash with water, aqueous sodium bicarbonate, water again and brine,
Dry over anhydrous magnesium sulphate and finally concentrate. The polymerizable residue was bubble-to-bulb distilled under vacuum of 0.2 mm and 210 ° C.
Illation). The unreacted starting material is then removed by distillation (at 0.01 mm, at 160 ° C.) to give 45 g of the title mixture as a yellow oil.

Example 12 5-Phenylthio-2- (2-hydroxy-3,5-di
Alkylphenyl) -2H-benzotriazole (al
The kill groups are independently C ₄ , C ₈ , C ₁₂ and C ₁₆ )
The mixture of granulated title, according to the method of Example 4, a mixture of Example 11 40 g, potassium hydroxide 11.2g and 1
Produced using 2.3 mL of thiophenol.

Example 13 5-benzenesulfonyl-2- (2-hydroxy-3,
5-dialkylphenyl) -2H-benzotriazole
(Alkyl groups are independently C ₄ , C ₈ , C ₁₂ and C ₁₆
Crude product of Example 12 of that), dropwise isopropanol 350 mL, the mixture of concentrated sulfuric acid formic acid and 1.8mL of 14.7 mL, heated to reflux, for 2 hours 50% hydrogen peroxide 30mL And add. After refluxing for an additional 3 hours, the reaction mixture is cooled and 10% sodium sulfite and aqueous sodium bicarbonate are added. The isopropanol is evaporated and the residue is extracted with methylene chloride.
The organic layer is washed with water and then dried over anhydrous magnesium sulfate. Concentrate the solution to give 45 g of crude product as a viscous red-yellow oil. About 30 g of this crude product was chromatographed on silica gel (heptane: ethyl acetate,
Purification by 4: 1) gives 28.9 g of the title mixture as a yellow oil.

Example 14 5-Diphenylphosphinyl-2- (2-hydroxy-
3,5-di-tert-butylphenyl) -2H-ben
Zotoriazoru condenser, and a flame-dried with a magnetic stirring bar and a thermometer 50
To a 0 mL three-necked round bottom flask, 100 mL of dimethyl sulfoxide, 7.41 g (0.066 mol) of potassium tert-butoxide and 11.17 g (0.060 mol) of diphenylphosphine are added via syringe. 10.56 in 50 mL of dimethyl sulfoxide
g (0.030 mol) of 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H
Add the benzotriazole together all at once to the red mixture. The resulting brown solution is stirred at 135 ° C. for 3.5 hours and then cooled to room temperature. The mixture is quenched with a portion of a saturated ammonium chloride solution and ethyl acetate is added. The organic layer is separated and washed with water 3
Wash once and once with brine, then dry over anhydrous magnesium sulfate. An exothermic reaction occurs when 50% hydrogen peroxide is added to the solution. The mixture is left for 30 minutes, then washed once with 10% sodium pyrosulfite solution, three times with saturated sodium bicarbonate solution, once with brine and finally dried over anhydrous magnesium sulfate. The mixture was filtered through a plug of silica gel, and the solvent was distilled off under reduced pressure to obtain 8.0 g.
To give a crude yellow solid. The crude product was purified by medium pressure chromatography using heptane: ethyl acetate = 1: 1, 4.2 g as a yellow solid melting at 98-100 ° C.
(27% yield) of the title compound is obtained.

Example 15 5-Diphenylphosphinyl-2- (2-hydroxy-
3-α-cumyl-5-tert-octylphenyl)-
2H-Benzotriazole Following the procedure of Example 14, the title compound was converted to 5-chloro-2- (2-hydroxy-3-α-cumyl-5-ter
Prepared when (t-octylphenyl) -2H-benzotriazole is used as the starting benzotriazole intermediate.

EXAMPLES 16-26 Following the general procedure of Example 1, the following additional formula I '
H-benzotriazole is produced.

[Table 1]

Example 27 5-octylthio-2- (2-hydroxy-3-α-octane
Mill-5-tert-octylphenyl) -2H-ben
Preparation of zotriazole 5-chloro-2- (2-hydroxy-3-α-cumyl-
Example 6 using 5-tert-octylphenyl) -2H-benzotriazole and octyl mercaptan
To produce the title compound.

Example 28 5-octylsulfonyl-2- (2-hydroxy-3-
α-cumyl-5-tert-octylphenyl) -2H
Preparation of -Benzotriazole 5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H -benzotriazole prepared in Example 27 was purified without purification of the thio intermediate. Oxidate to the sulfone using the general method of Example 7.

Example 29 5-Chloro-2- (2,4-dihydroxyphenyl)-
Preparation of 2H-benzotriazole In accordance with parts a) and b) of the general method of Example 1, the monoazo intermediate of the title compound was obtained by adding 17.3 g of 4-chloro-2-
There are obtained 34.7 g of a wet cake of the deep red monoazo adduct prepared from nitroaniline.

Reduction of the monoazo adduct A mixture of 20 g of sodium hydroxide, 500 mL of water and the wet cake of 26.3 g of the monoazo adduct prepared above is heated to 30 ° C. Zinc powder (33.0 g) is added in portions over 2 hours. After this addition, 180
g of a 40% aqueous sodium hydroxide solution are added dropwise over 1 hour. The mixture is stirred at ambient temperature for 96 hours. The zinc residue is removed by filtration. Neutralize the aqueous solution to pH 5-6 and filter the resulting slurry and filter the resulting slurry. The resulting filter cake is thoroughly dried with water,
Dry to obtain 22.5 g of crude product. The crude product is purified by Soxhlet extraction using acetone to give 9.6 g of the title compound.

Example 30 5-Chloro-2- (2-hydroxy-4-octyloxy)
(Ciphenyl) -2H-benzotriazole 6.5 g of 5-chloro-2- (2,4-dihydroxyphenyl) -2H -benzotriazole, 7.1 g of 1-
Bromooctane, 5.2 g of anhydrous potassium carbonate and 100
Reflux the mixture of mL acetone for 24 hours. To the resulting mixture, add about 100 mL of water and ethyl acetate,
10.6 g of crude product are isolated. Column chromatography using petroleum ether showed that the structure was Hn
This gives 0.9 g of the title compound as determined by mr and mass spectrum.

Example 31 5-trifluoromethyl-2- (2,4-dihydroxy
Preparation of phenyl) -2H-benzotriazole Following the general procedure of Example 29, the title compound was obtained from 10.
Prepared from 3 g of 4-amino-3--3-nitrobenzotrifluoride to give 6.4 g of the title compound whose structure has been confirmed by Hnmr.

Example 32 5-trifluoromethyl-2- (2-hydroxy-4-
Octyloxyphenyl) -2H-benzotriazole
The title preparation of the compounds according to the general method of example 30, 5.
Prepared from 6 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole. The crude product is purified by column chromatography to give 1.1 g of the title compound as a white solid melting at 79-81 ° C. Its structure is determined by Hnmr and mass spectrum.

Example 33 5-trifluoromethyl-2- [2-hydroxy-4-
(Butoxy-2-hydroxypropoxy) phenyl]-
Preparation of 2H-benzotriazole 2.3 g of 5 in Example 31 in 50 mL of xylene
-Trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 1.3 mL of butyl glycidyl ether and 100 mg of ethyltriphenylphosphonium bromide are heated to reflux under nitrogen for 14 hours. Add water (25 mL) and 25 mL of ethyl acetate and isolate 3 g of crude product. Recrystallization from heptane gives 2.1 g of the title compound whose structure is determined by nmr.

Example 34 5-trifluoromethyl-2- (2-hydroxy-4-
Preparation of (aminophenyl) -2H-benzotriazole The title compound is prepared according to the general method of Example 1 and Example 29, starting from 4-amino-3-nitrobenzotrifluoride and 3-aminophenol. . The structure of the product is determined by nmr.

Example 35 5-trifluoromethyl-2- [2-hydroxy-4-
(2-ethylhexanoylamino) phenyl] -2H-
Preparation of benzotriazole 4 g of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2 in 75 mL of toluene
To a mixture of H-benzotriazole and 1.4 g of triethylamine is added dropwise a mixture of 2-ethylhexanoyl chloride in 125 mL of toluene. The resulting mixture was treated with 100 mL of water and the resulting crude product was purified by column chromatography,
1.9 g of the title compound melting at 9-181 ° C. are obtained. Its structure is determined by nmr.

Example 36 5-Carbomethoxy-2- (2-hydroxy-3-α-
Cumyl-5-tert-octylphenyl) -2H-be
Preparation of Nzotriazole a) Esterification of 4-amino-3-nitrobenzoic acid In a 2 L three-necked flask equipped with a mechanical stirrer, 700 mL of methanol, 20 g of xylene, 14 g of concentrated sulfuric acid and 10 g of
0 g of 4-amino-3-nitrobenzoic acid are added. Heat the solution to reflux for 33 hours. Cool the mixture to 35 ° C. and neutralize to pH 7.8. Add water (1 L),
After collecting the solid and washing with 500 mL of water and drying overnight, 100.9 g of 4-amino-3-nitrobenzoic acid methyl ester are obtained.

B) Diazotization of 4-amino-3-nitrobenzoic acid methyl ester In a 1 L three-necked flask equipped with a mechanical stirrer, 177 g of 9
Add 6% sulfuric acid, then slowly add 11 g sodium nitrite over 90 minutes. The mixture is heated to 30 ° C. to initiate the reaction. Keep the temperature below 70 ° C.
The mixture is then cooled to 15 ° C. and 30 g of 4
-Amino-3-nitrobenzoic acid methyl ester is added over 2 hours keeping the temperature between 15-20 ° C. The mixture is cooled to 0 ° C. and 200 g of ice are added to make the solution suitable for the coupling reaction to form the monoazo compound.

C) Monoazo adduct In a 2 L three-necked flask equipped with a mechanical stirrer and an addition funnel,
52 g of 2-α-cumyl-4-tert-octylphenol, 20 g of water, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide are charged. The mixture is cooled to −5 ° C. and the diazonium salt solution prepared in step b) is added over 2 hours while cooling and keeping the temperature below 3 ° C. After adding the diazonium salt solution,
Adjust the pH to 6.5-7.0. 500 times the mixture
Pour into mL xylene and wash 3 times with 500 mL water at 60 ° C. The xylene is removed by distillation, yielding 186 g of monoazo adduct containing residual xylene.

D) Reduction of the monoazo adduct In a 500 mL flask equipped with a mechanical stirrer, 186 g of the monoadduct prepared in step c), 125 g of 2-butanol and 1.7 g of 2,3-dichloro-1,4 -Add naphthoquinone. Heat the mixture to 90 ° C. and then place the resulting solution in an addition funnel on a second flask. In the second flask described above, 175 g of 2-butanol and 1
8.6 g of sodium hydroxide are added. The flask is heated to 95 ° C. and the monoazo solution is added over 2 hours, during which the methyl ethyl ketone and 2-butanol are distilled off. Then 2-butanol (100 g) is added and the azeotropic distillate is distilled off. Then cool the mixture to 300 g
Of xylene and 200 mL of water are added. Adjust the pH to 7-7.5 using 20% sulfuric acid. Separate the aqueous phase at 60 ° C. and wash the organic phase twice with 200 mL of water.
7. Xylene is distilled off, and the resulting residue is recrystallized from methanol to melt at 141 to 143 ° C.
8 g are obtained.

Example 37 5-N, N-di-n-butylcarbamoyl-2- (2-
Hydroxy-3-α-cumyl-5-tert-octyl
Preparation of phenyl) -2H-benzotriazole a) 5-carbomethoxy-2- (2-hydroxy-3-
α-cumyl-5-tert-octylphenyl) -2H
-Saponification of benzotriazole 25 with mechanical stirrer, thermometer, condenser and nitrogen inlet
To a 0 mL three-necked flask, add 1.8 g potassium hydroxide and 40 mL methanol. Heat the mixture to 40 ° C. to dissolve the potassium hydroxide. 40 m in this solution
2.7 g of 5 prepared in Example 36 in 5 L of methanol
-Carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole is added. The reaction mixture is refluxed for 6 hours. The mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl acetate are added, then the organic layer is separated and dried over anhydrous sodium sulfate. After vacuum stripping the solvent, 2.5 g of 5-carboxy-2- (2-
Hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole is isolated.

B) 5-chlorocarbonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole 2.5 g of 5-carboxy-2 prepared in step a) −
(2-Hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole was charged with a stirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogen inlet. Into a 250 mL three-necked flask equipped with Toluene (1
(00 mL) and the mixture is refluxed to remove traces of water. The mixture is then cooled and 0.76 g of oxalic acid chloride in 15 mL of toluene is added. The reaction mixture is heated slowly to 60 ° C. and kept at 60-65 ° C. for 8 hours until all the hydrogen chloride has been exhausted, giving the acid chloride of the title compound.

C) 5-N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-α-cumyl-5-t
ert-octylphenyl) -2H-benzotriazole 50 with mechanical stirrer, drying tube, thermometer and dropping funnel.
To a 0 mL flask, add 0.8 g di-n-butylamine, 6 mL pyridine and 25 mL toluene. The mixture is cooled to 0 ° C, the acid chloride prepared in step b) is placed in a dropping funnel and added to the reaction mixture at -5 ° C to -10 ° C over 30 minutes. The reaction mixture is stirred at that temperature for 1.5 hours, then kept at ambient temperature overnight. The mixture is filtered and then vacuum stripped to give 3.0 g of a crude solid. Chromatography of the solid product gives 1.2 g of the title compound as a tan solid melting at 131-133 ° C. Structure is nm
r and mass spectrum m / z 596.

Example 38 5-trifluoromethyl-2- (2-hydroxy-5-
tert-octylphenyl) -2H-benzotriazo
The title compound is prepared from the diazo compound of 4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol according to the general method of Example 1,
The title compound is purified by chromatography on silica gel. Recrystallization of the product from either heptane or methanol gave the title compound at 80-81 ° C.
To give an almost white solid that melts.

Use Example 39 The thermal durability and loss rate of various 2H-benzotriazole UV absorbers substituted with various electron withdrawing or electron donating groups from high solids thermoset acrylic coatings were determined. In order to do so, the following test is conducted.

The high solid thermosetting acrylic transparent paint is produced by mixing an experimental acrylic polyol resin with hexamethoxymethylmelamine (registered trademark 747, Monsanto) at a solid content ratio of 60/40. Dodecylbenzene sulfonic acid catalyst ((registered trademark) Nacure 5225, King Industry)
is) is added at 0.7% by weight. Flow Aid® Modaflow was added at 0.25% by weight,
Form the model acrylic melamine resin system.

The model transparent paint was Zahn # with xylene.
Dilute to a viscosity of 26-27 seconds using 2 cups and use normal air spray to 50 psi (3.5 Kg / c
m ² ), 1 ″ × 3 ″ (2.54 cm × 7.62 cm)
Sprinkle on a quartz slide. For curing, bake the slides at 260 ° F. (127 ° C.) for 30 minutes. Transparent paint
1% by weight of a hindered amine light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate® TINUVIN1
23, Ciba-Geigy). Various test benzotriazole UV absorber 5m in transparent paint
It is blended in mol% by weight. The thickness of the coating on the quartz slide is 1.15 to 1.41 mils (0.
029 to 0.036 mm).

The film on the quartz slide was coated with an internal quartz and an external borosilicate in a xenon arc weatherometer with controlled irradiance at 6500 W according to the following conditions:
Expose using an S-type filter. The irradiation cycle is as follows: linear irradiation without water spray for 40 minutes, followed by 20 minutes light plus front spray (from
nt spray), followed by 60 minutes of light irradiation and finally 60 minutes of dart plus rear spray. The settings are 0.55 W / M ^{2 at} 340 nm and 1.98 kJ / hour. In the light cycle, the temperature of the black panel is controlled at 70 ± 2 ° C. The relative humidity in the light cycle is in the range of 50-55% and 100% in the dark cycle. The absorbance of the long wavelength UV band as a function of the xenon arc exposure time is described in the table below.

To track the loss of UV absorber from the clear coating, the UV spectrum is measured initially and at regular time intervals after exposure. UV spectrophotometers are based on a reference beam dilution technique.
The absorbance is measured linearly up to 5.5 absorbance units using the T.I.

It is assumed that the decomposition products from the UV absorber do not contribute to the UV spectrum. This is about 300nm
Tested by tracking the ratio of the absorbance at 340 nm to the absorbance at 340 nm. This ratio does not change when the sample is exposed. This implies that the UV spectrum of the exposed film (coating) corresponds to the amount of UV absorber remaining in the film, but the contribution of the photolysis products to the spectrum is very small. I have.

The data in the table below shows the exposure 1211 of the clear coating containing the test benzotriazole UV absorber.
Based on structural formula A after time, where G ₁ is H.

[Table 2]

A closer inspection of these data leads to certain clear conclusions about the photostability of 2H-benzotriazoles and the nature of the substituents that affect their photostability.

Increased stability occurs when R ₁ is a cumyl or phenyl group and G ₂ is an electron withdrawing group such as a phenylsulfonyl or cyano group.

The nature of the R ₂ group has little effect on the photostability of the benzotriazole UV absorber.

From these observations, the idealized benzotriazole ultraviolet absorber shows that G ₂ is an electron withdrawing group,
It can be designed theoretically when R ₁ is an effective bulky group and R ₂ is a thermally stable moiety. One such idealized compound is that G ₂ is a phenylsulfonyl group, R ₁ is an α-cumyl group, and R ₂ is
It is a benzo-triazole which is an ert-octyl group.
The benzotriazole is generally disclosed in U.S. Pat.
5,280,124. Example 4 below
The data set forth at 0 confirm this prediction and the "idealized" compound actually shows a much lower rate of loss than the state of the art.

Example 40 Use Following the general procedure of Example 39, additional benzotriazole test compound is made into a high solids thermoset acrylic melamine resin at equivalent film thickness and equivalent molar concentration of test benzotriazole. And enough for the initial absorbance to be about 2.0 units,
Formulated at a concentration between 1.93% and 3% by weight.

The test disk was set for × 180 cycles (0.45
Watts / M ² ) in a xenon-arc weatherometer. The first UV absorbance is measured, then the first 2000 hours are at approximately 250 hour intervals and then 5
Measure every 00 hours. Each clear coating also contains 1% by weight of a hindered amine light stabilizer, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The data in the table below is based on the compound of Formula A (where G ₁ is a hydrogen atom) after exposing the clear coating containing the test benzotriazole UV absorber for 1253 hours. is there.

[Table 3]

The data in the table below is based on the compound of formula A (where G ₁ is a hydrogen atom) after exposing the clear coating containing the test benzotriazole UV absorber for 1489 hours. is there.

[Table 4]

The data in the table below is based on the compound of formula A (where G ₁ is a hydrogen atom) after exposing the transparent coating containing the test benzotriazole UV absorber for 2521 hours. is there.

[Table 5]

From the above three tables, it is clear that compounds S and especially T having an electron withdrawing group on the benzo ring are significantly superior to benzotriazoles having no such group on the benzo ring.

The data in the table below is based on the compound of Formula A (where G ₁ is a hydrogen atom) after exposing the clear coating containing the test benzotriazole UV absorber for 1264 hours. is there.

[Table 6]

The data in the table below is based on the compound of Formula A (where G ₁ is a hydrogen atom) after exposing the clear coating containing the test benzotriazole UV absorber for 1518 hours. is there.

[Table 7]

The data in these tables indicate that benzotriazoles in which the benzo ring is substituted by an electron-withdrawing group, especially a group such as a trifluoromethyl or phenylsulfonyl group, are measured after exposure to actinic radiation. As noted, a low loss of absorbance value indicates that it is particularly durable. Compounds S, U, V and W are particularly durable and meet the profile proposed above. Indeed, the prediction that Compound U is particularly durable was born from the above data. Inspection of the data for compounds T and U, as compared with mere alkyl moiety such as tert- butyl position of R _1, with valid bulky groups such as α- cumyl the R ₁ position It shows an additional beneficial effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 3/00 104 C09K 3/00 104C // C07D 249/20 502 C07D 249/20 502 (72) Inventor Ansonii David Develis United States of America, New York 10923, Gamaville, Frederick Street 29 (72) Inventor Lebasi Enger United States of America, New York 10566, Coatland Maynoa, Jerome Draive 33 (72) Inventor Joseph Saddlenik United States of America, New York 10598, Yorktown Heights, Hallox Mill Road 337 (72) Inventor Jean-Pierre Wolff Switzerland, 1791 Kurtaman, Shemin de la Motta 257 (72) Inventor Robert Edward de Treffsen United States, New York 10579, Putnam Valley, Somerset Lane 37 (72) Inventor Marvin Gale Wood United States, New York 12570, Pouquag, Beach Road, Rural Earl 1 Box 366 Ay

Claims (25)

[Claims] 1. A coating composition stabilized with benzotriazole, said benzotriazole exhibiting enhanced durability and low loss rate when incorporated into said composition; (A) a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin having a carbamate side group crosslinked with melamine, or an acrylic polyol resin crosslinked with melamine containing a carbamate group 0.01 to 5% by weight, based on the resin solids, of the resin selected and (b) the resin A, B, C or D Wherein G ₁ , G ₂ or T represents an electron withdrawing group; G ₁ represents a hydrogen atom or a halogen atom; G ₂ represents a halogen atom, a nitro group, a cyano group, R ₃ SO—, R ₃ SO ₂ -, -COOG
_{3, CF 3 -, - P} (O) (C 6 H 5) 2, -CO-G
_{3, -CO-NH-G 3} , -CO-N (G 3) 2, -N
(G ₃ ) -CO-G ₃ , G ₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, and 5 to 1 carbon atoms.
2 cycloalkyl group, phenylalkyl group having 7 to 15 carbon atoms, phenyl group, the above phenyl group substituted by 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the above phenylalkyl group Represents; R ₁
Represents a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, C 7 -C 15 phenylalkyl, phenyl, C 1 -C 4 on the phenyl ring
Represents the above phenyl group or the above phenylalkyl group substituted with 1 to 4 alkyl groups; R ₂ represents a hydrogen atom,
A straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms,
A phenylalkyl group having 7 to 15 carbon atoms, a phenyl group, the above phenyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the above phenylalkyl group, or R ₂ It is (wherein, R ₄ represents a linear or branched alkyl group having 1 to 24 carbon atoms.) a hydroxyl group or -OR _4; 1 or more -OH, -OCO-R _11, -O
R ₄ , —NCO or —NH ₂ or the above alkyl group substituted by a mixture thereof; or one or more —O—, —N
H- or -NR ₄ - groups or it is interrupted by a mixture thereof, and unsubstituted or one or more -OH, -OR ₄
Or R ₂ represents an alkyl group or an alkenyl group optionally substituted by an —NH ₂ group or a mixture thereof; or R ₂ represents —SR ₃ , —NHR ₃ or —N (R ₃ ) ₂
Or R ₂ is — (CH ₂ ) _m —CO—X— (Z) _p —
Y-R ₁₅ [wherein, X represents -O- or -N (R ₁₆ )-, Y represents -O- or -N (R ₁₇ )-, and Z represents an alkylene having 2 to 12 carbon atoms. Represents an alkylene group having 4 to 12 carbon atoms interrupted by a group, 1 to 3 nitrogen atoms, oxygen atoms or a mixture thereof, or an alkylene group having 3 to 12 carbon atoms, butenylene group, butynylene group, Represents a cyclohexylene group or a phenylene group, each of which is substituted by a hydroxyl group, m represents 0, 1 or 2, p represents 1, or X and Y each represent -N (R ₁₆₎ - and -N (if a R ₁₇₎ 0 also represents, R ₁₅ is a group _{-CO-C (R 18) =} C (H) or represents a R _19, Y is -N (R ₁₇₎ -Represents a group together with R _17-
R ₁₈ represents a hydrogen atom or a methyl group, and R ₁₉ represents a hydrogen atom, a methyl group or —CO—X—R ₂₀
R ₂₀ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a formula (Wherein, symbols G ₁ , G ₂ , R ₁ , X, Z, m and p have the same definitions as above), and R ₁₆ and R ₁₇ independently represent a hydrogen atom, a carbon atom number of 1 Represents a C 12 -C 12 alkyl group, a C 3 -C 12 alkyl group interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or a C 7 -C 15 aralkyl group, and Z is When R ₁₆ represents an ethylene group, it together with R ₁₇ also forms an ethylene group. N is 1 or 2
And when n represents 1, R ₅ is Cl, OR ₆ or NR ₇ R
₈ or R ₅ is —PO (OR ₁₂ ) ₂ , —OSi
(R ₁₁ ) ₃ represents —OCO—R ₁₁ , or represents —O—,
-S- or -NR ₁₁ - be interrupted by, and unsubstituted or -OH or an alkyl group of 24 to 1 carbon atoms, --OCO-R ₁₁ which may linear or also be branched substituted; An unsubstituted or -OH substituted C 5 -C 12 cycloalkyl group; an unsubstituted or -OH substituted linear or branched C 2 -C 18 alkenyl group, Represents an aralkyl group having 7 to 15 carbon atoms, —CH ₂ —CHOH—R ₁₃ or a glycidyl group; R ₆ is a hydrogen atom, unsubstituted or 1
Represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms which is substituted by at least one OH, OR ₄ or NH ₂ group, or —OR ₆ is — (OCH ₂ CH ₂ ) _w O
H or — (OCH ₂ CH ₂ ) _w OR ₂₁ , wherein w represents 1 to 12 and R ₂₁ represents an alkyl group having 1 to 12 carbon atoms; R ₇ and R ₈ are independent of each other A hydrogen atom, an alkyl group having 1 to 18 carbon atoms;
A straight-chain or branched C 3 -C 18 alkyl group interrupted by —O—, —S— or —NR ₁₁ —,
A cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms or 1 to 3 carbon atoms
Or R ₇ and R ₈ are N
Together with the atom represents a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring; when n represents 2, R ₅ represents a divalent group —O—R ₉ —O— or —N (R ₁₁ )
—R ₁₀ —N (R ₁₁ ) —; R ₉ represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, an alkynylene group having 4 carbon atoms, a cyclohexylene group. , -O- or -CH ₂ -CHOH-CH _{2
-O-R 14 -O-CH 2} -CHOH-CH 2 - C 4 -C straight or branched chain which is interrupted by 1
0 represents an alkylene group, and R ₁₀ represents a linear or branched alkylene group having 2 to 12 carbon atoms which may be interrupted by —O—, a cyclohexylene group or Or R ₁₀ and R ₁₁ together with two nitrogen atoms form a piperazine ring; R ₁₄ is a linear or branched C 2 -C 8 alkylene group, —O— A straight-chain or branched-chain alkylene group having 4 to 10 carbon atoms, a cycloalkylene group, an arylene group or R ₇ and R ₈ are independently a hydrogen atom or a carbon atom having 1
Or R ₇ and R ₈ together represent an alkylene group having 4 to 6 carbon atoms, 3-oxapentamethylene group, 3-iminopentamethylene group or 3-methyliminopentamethylene. R ₁₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms,
R ₁₂ represents a straight-chain or branched alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 15 carbon atoms; An alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 18 carbon atoms,
A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms or 7 to 1 carbon atoms
5 represents an aralkyl group; R ₁₃ is H, —PO (O
R ₁₂ ) a straight-chain or branched alkyl group having 1 to 18 carbon atoms substituted by ₂ ; an unsubstituted or substituted OH-substituted phenyl group;
Represents aralkyl group or -CH ₂ OR _12; R ₃ is alkyl of 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, C 3 -C 1
An alkenyl group having 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, or one or two alkyl groups having 1 to 4 carbon atoms. L represents an alkylene having 1 to 12 carbon atoms, wherein said aryl group or perfluoroalkyl moiety substituted by is a 1,1,2,2-tetrahydroperfluoroalkyl group having 6 to 16 carbon atoms; Group, 2 to 1 carbon atoms
2 represents an alkylidene group, a benzylidene group, a p-xylylene group or a cycloalkylidene group, and T represents -SO
_{-, - SO 2 -, -} SO-E-SO -, - SO 2 -E-
SO _2- , -CO-, -CO-E-CO-, -COO-
E-OCO -, - CO- NG 3 -E-NG 3 -CO- or _{-NG 3 -CO-E-CO-} NG 3 - ( alkylene group in the formula, E is 2 -C atoms 12, carbon atoms A cycloalkylene group having 5 to 12 carbon atoms or a cyclohexylene group having 8 to 12 carbon atoms, or an alkylene group terminated by the same). Consisting of a benzotriazole represented by｝; the benzotriazole in the xenon arc weatherometer
Demonstrated by a loss of less than 0.22 absorbance units after 200 hours of exposure, or less than 0.27 absorbance units after 1500 hours of exposure, or less than 0.40 absorbance units after 2500 hours of exposure. Thus, a composition that exhibits enhanced durability and low loss rates when the coating is exposed to actinic radiation. 2. Component (b) has the formula A ′ (Wherein, G ₂ is a fluorine atom, a chlorine atom, a cyano group, R ₃ SO
_{2 -, CF 3 -, -} CO-G 3, -COO-G 3 or -
CO-N (G ₃ ) ₂ ; G ₃ represents 1 to 1 carbon atoms
2 represents an alkyl group; R ₁ is a hydrogen atom, having 1 carbon atom
To 12 alkyl groups, phenyl groups, phenylalkyl groups having 7 to 15 carbon atoms or the above-mentioned phenyl groups or phenylalkyl groups in which the phenyl ring is substituted by 1 or 2 alkyl groups having 1 to 4 carbon atoms R ₂ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or —CH ₂ CH ₂ COOG ₄ (wherein G ₄ is a hydrogen atom, a carbon atom number; Substituted by 1 to 24 alkyl groups or OH, interrupted by 1 to 6 -O- atoms or substituted by OH and interrupted by 1 to 6 -O- atoms are represents an alkyl radical as defined above and R ₃ is 1-alkyl group, the number aryl group or a carbon atom of 6 to 10 carbon atoms of 1 to 18 carbon atoms The composition of claim 1 wherein the compound represented by the representative.) The aryl group substituted with an alkyl group 1 or 2 of stone 4. 3. The compound of the formula A ′, wherein G ₂ is a fluorine atom, a chlorine atom, a cyano group, R ₃ SO _{3
2 -, CF 3 -, -} COO-G 3 or -CO-N (G _3)
2 represents; G ₃ represents an alkyl group of 1 to 8 carbon atoms; R ₁ is a hydrogen atom, a phenyl group or α- cumyl represents a group; R ₂ is an alkyl group or a phenyl group having 12 C 4 -C _3. A composition according to claim 2, wherein R ₃ represents phenyl or an alkyl group having 8 to 12 carbon atoms. Wherein G ₂ is phenyl -SO ₂ -, octyl -S
O ₂ -, a fluorine atom or CF ₃ - a represents: represents R ₁ is α- cumyl or phenyl group, and R ₂ is tert-
The composition according to claim 3, which represents a butyl group or a tert-octyl group. 5. The composition according to claim 1, wherein the component (a) is a resin which is a thermosetting acrylic melamine resin or an acrylic urethane resin. 6. N-octadecyl 3,5-di-tert
-Butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis (3,5-di-tert
-Butyl-4-hydroxyhydrocinnamate), di-
n-octadecyl 3,5-di-tert-butyl-4
-Hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinna) Mate), 1,3,5-trimethyl-2,4,
6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-butyl-4)
-Hydroxyhydrocinnamate), 2,6-di-te
rt-butyl-p-cresol, 2,2′-ethylidene-bis (4,6-di-tert-butylphenol),
1,3,5-tris (2,6-dimethyl-4-tert
-Butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1,3
5-tris [2- (3,5-di-tert-butyl-4)
-Hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3,5-di- (3,5-di-tert-
Butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5-di-tert-butyl-4-)
Hydroxyhydrocinnamate), 1- (3,5-di-
tert-butyl-4-hydroxyanilino) -3,5
-Di (octylthio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-
4-hydroxyhydrocinnamamide), calcium
Bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis [3
3-di (3-tert-butyl-4-hydroxyphenyl) butyrate], octyl 3,5-di-tert-
Butyl-4-hydroxybenzylmercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N′-bis [2- (3,5-di-tert-butyl- The composition according to claim 1, further comprising a stabilizing amount of a phenolic antioxidant selected from the group consisting of 4-hydroxyhydrocinnamoyloxy) -ethyl] -oxamide. 7. A phenolic antioxidant comprising neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4. -Hydroxyhydrocinnamate, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-
(Hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2′- The composition according to claim 6, which is ethylidene-bis (4,6-di-tert-butylphenol). 8. Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,2)
6,6-pentamethylpiperidin-4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) Butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9 -Tetramethyl-1,3,8-triazaspiro [4.5] decane-
2,4-dione, tris (2,2,6,6-tetramethyl-4-piperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,4,4-tetramethyl-
3-oxopiperazin-4-yl) ethane, 2,2
6,6-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5.1.11.2] heneicosane, 2,4-dichloro-6-tert-octylamino-s-triazine and 4, 4'-Hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine)
Polycondensation product with 1- (2-hydroxyethyl)-
Polycondensation product of 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 1 Polycondensation product with 2,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2 , 6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, 2,4-dichloro-6-yl
Polycondensation product of morpholino-s-triazine and 4,4′-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ′, N ″, N ″ ′-tetrakis [ (4,6-bis (butyl-1,2,2,6,
6-pentamethylpiperidin-4-yl) -amino-s
-Triazin-2-yl] -1,10-diamino-4,
7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl / β, β, β ′, β′-tetramethyl-3,9,-(2,4,8,10- Tetraoxaspiro [5.5] -undecane) diethyl] 1,
2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidine-4-
Yl / β, β, β ′, β′-tetramethyl-3,9-
(2,4,8,10-tetraoxaspiro [5.5]-
Undecane) diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis (2,2,
6,6-tetramethylpiperidine-4-carboxylate), 4,4′-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N- (2,2,6,
6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl -2,2,6,6-tetramethylpiperidin-4-yl n-dodecylsuccinimide, 1
-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-
2,4-dione, di- (1-octyloxy-2,2,
6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6,
6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-te
rt-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,
6-tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2,
2,6,6-tetramethylpiperidin-4-yl) imino] and 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-
The composition according to claim 1, further comprising an effective stabilizing amount of a hindered amine selected from the group consisting of 4-yl) -n-butylamino] -s-triazine. 9. The hindered amine is bis (2,2,6,6)
-Tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine-4)
-Yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert
-Butyl-4-hydroxybenzyl) butylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-
Polycondensation products of tetramethyl-4-hydroxypiperidine and succinic acid, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylenebis (amino-2,2,6 , 6-tetramethylpiperidine), N, N ', N ", N"'-
Tetrakis [(4,6-bis (butyl-1,2,2,2
6,6-pentamethylpiperidin-4-yl) -amino-s-triazin-2-yl] -1,10-diamino-
4,7-diazadecane, di- (1-octyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)
Sebacate, di- (1-cyclohexyloxy-2,
2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-
{[6-tert-octylamino-s-triazine-
2,4-diyl] [2- (1-cyclohexyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)
Imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4
-Yl) imino] or 2,4,6-tris [N- (1-
The composition according to claim 8, which is cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine. 10. The composition according to claim 1, further comprising another ultraviolet absorber selected from the group consisting of s-triazines, oxalic anilides, hydroxybenzophenones, benzoates and α-cyanoacrylates. Stuff. (11) a composition comprising 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,4-diphenyl-6- (2 -Hydroxy-4-hexyloxyphenyl) -s-triazine; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do-
/ Tri-decyloxy-2-hydroxypropoxy) phenyl] -s-triazine or 2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-
The composition according to claim 10, further comprising s-triazine, which is cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -s-triazine. 12. A compound of the formula I, II, III or IV G ₁ represents a hydrogen atom or a halogen atom; G ₂ represents a cyano group, E ₃ SO—, E ₃ SO ₂ —, —COOG ₃ , CF ₃
-, - P (O) ( C 6 H 5) 2, -CO-G 3, -CO
-NH-G ₃ or -CO-N (G ₃₎ represents _2; G ₃ is a straight-chain or branched alkyl group having 1 to 24 carbon atoms, straight-chain or branched C 2 -C 18 An alkenyl group of a chain, a cycloalkyl group having 5 to 12 carbon atoms,
Phenylalkyl 15 to 7 carbon atoms, a phenyl group, to no alkyl group 1 C1 -C4 on the phenyl ring represent the phenyl group or the phenyl group substituted by four; E ₁ is hydrogen represents atoms, phenylalkyl of 7 to 15 carbon atoms, a phenyl group, not an alkyl group 1 C1 -C4 on the phenyl ring to the phenyl group substituted with four or said phenylalkyl group; E ₂ Is a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and 7 carbon atoms. 1 to 15 phenylalkyl groups, phenyl groups and 1 carbon atom on the phenyl ring
Represents the above phenyl group or the above phenylalkyl group substituted with 1 to 3 alkyl groups, or E ₂ represents a hydroxyl group or —OE ₄ , wherein E ₄ is a straight-chain having 1 to 24 carbon atoms. represents a chain or branched alkyl groups);. 1 or more -OH, -OCO-E _11, -O
The above alkyl group substituted by E ₄ , —NCO or —NH ₂ or a mixture thereof; or one or more —O—, —N
H- or -NE ₄ - groups or and is interrupted by the mixing thereof unsubstituted or one or more -OH, -OE ₄ or -NH ₂ groups or alkyl which may above substituted by mixtures thereof Represents a group or an alkenyl group as described above;
Or E ₂ represents —SE ₃ , —NHE ₃ or —N (E ₃ ) ₂ ; or E ₂ represents — (CH ₂ ) _m —CO—X— (Z) _p —Y—
E ₁₅ [wherein, X represents —O— or —N (E ₁₆ ) —, Y represents —O— or —N (E ₁₇ ) —, Z represents an alkylene group having 2 to 12 carbon atoms, Represents an alkylene group having 4 to 12 carbon atoms interrupted by 1 to 3 nitrogen atoms, oxygen atoms or a mixture thereof, or an alkylene group having 3 to 12 carbon atoms, butenylene group, butynylene group, cyclohexylene group or an group, each a phenylene group is substituted by a hydroxyl group, m is 0, 1 or 2, or p is 1, or X and Y each is -N the (E ₁₆₎ - If a and -N (E ₁₇₎ 0 also represents, E ₁₅ is or represents a group _{-CO-C (E 18) =} C (H) E 19, Y is -N (E ₁₇₎ - a When represented, the group together with E ₁₇
E ₁₈ represents a hydrogen atom or a methyl group, and E ₁₉ represents a hydrogen atom, a methyl group or —CO—X—E ₂₀
E ₂₀ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a compound represented by the formula: (Wherein, symbols G ₁ , G ₂ , E ₁ , X, Z, m and p have the same definitions as above), and E ₁₆ and E ₁₇ independently represent a hydrogen atom, a carbon atom number of 1 Represents a C 12 -C 12 alkyl group, a C 3 -C 12 alkyl group interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or a C 7 -C 15 aralkyl group, and Z is E _{16 in the} case of representing an ethylene group together with E ₁₇ also forms an ethylene group. N is 1 or 2
When n represents 1, E ₅ is Cl, OE ₆ or NE ₇ E
₈ or E ₅ is —PO (OE ₁₂ ) ₂ , —OSi
(E ₁₁ ) ₃ represents —OCO—E ₁₁ , or represents —O—,
-S- or -NE ₁₁ - be interrupted by unsubstituted or C 1 -C good straight or branched chain optionally substituted by or -OCO-E ₁₁ -OH to 24 alkyl group; Not C5-C12 cycloalkyl substituted or substituted by -OH; unsubstituted or -O
A straight-chain or branched alkenyl group having 2 to 18 carbon atoms, which is substituted by H, 7 to 15 carbon atoms
Represents an aralkyl group, —CH ₂ —CHOH—E ₁₃ or a glycidyl group; E ₆ represents a hydrogen atom, a straight or substituted unsubstituted or substituted one or more OH, OE ₄ or NH ₂ groups. Represents a branched alkyl group having 1 to 24 carbon atoms, or -OE ₆ is-(OCH ₂ CH ₂ ) _w OH or-(OCH ₂ CH ₂ ) _w OE ₂₁ , wherein w is 1 to 12 And E ₂₁ represents an alkyl group having 1 to 12 carbon atoms); E ₇ and E ₈ independently of one another
A hydrogen atom, an alkyl group having 1 to 18 carbon atoms;
-, - S- or -NE ₁₁ - by alkyl group having 3 to carbon atoms and straight-chain or branched interrupted 18, cycloalkyl groups having 5 to 12 carbon atoms, 6 carbon atoms
N represents 14 to 14 aryl groups or C 1 to C 3 hydroxyalkyl groups, or E ₇ and E ₈ together with an N atom represent a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring; Represents 2
E ₅ represents a divalent group —OE ₉ —O— or —N (E ₁₁ ) -E
₁₀ -N (E ₁₁ )-; E ₉ represents an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, an alkynylene group having 4 carbon atoms, a cyclohexylene group,- O- or -CH ₂ -CHOH-CH ₂ -O
_{-E 14 -O-CH 2 -CHOH-} CH 2 - C 4 -C straight or branched chain which is interrupted by represents 10 alkylene, E ₁₀ is interrupted by -O- A straight-chain or branched alkylene group having 2 to 12 carbon atoms, a cyclohexylene group or Or E ₁₀ and E ₁₁ are taken together with two nitrogen atoms to form a piperazine ring, E ₁₄ is a linear or branched C 2 -C 8 alkylene group, —O— A linear or branched alkylene group having 4 to 10 carbon atoms, a cycloalkylene group, an arylene group or E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or E ₇ and E ₈ together represent an alkylene group having 4 to 6 carbon atoms, 3 - oxapentamethylene, 3-imino pentamethylene or 3-methyl imino pentamethylene the stands; E ₁₁ is hydrogen, straight or branched chain alkyl group of 1 to 18 carbon atoms of, C 5 -C 12 cycloalkyl groups, straight-chain or branched-chain alkenyl groups having 3 to 8 carbon atoms,
An aryl group having 6 to 14 carbon atoms or 7 carbon atoms
E ₁₂ represents a straight-chain or branched alkyl group having 1 to 18 carbon atoms, a straight-chain or branched alkenyl group having 3 to 18 carbon atoms, 5 carbon atoms. 10 to 10 cycloalkyl groups, 6 carbon atoms
No C 7 16 aryl group or a carbon atom to represent 15 aralkyl group; E ₁₃ is H, -PO (OE _{12) 2}
A straight-chain or branched alkyl group having 1 to 18 carbon atoms, an unsubstituted or substituted OH-substituted phenyl group, an aralkyl group having 7 to 15 carbon atoms or -CH ₂ OE _And E ₃ represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, The aryl or perfluoroalkyl moiety as defined above, which is substituted by one or two C 7 -C 15 phenylalkyl, C 6 -C 10 aryl or C 1 -C 4 alkyl, L represents a 1,1,2,2-tetrahydroperfluoroalkyl group having 16 carbon atoms; L represents an alkylene having 1 to 12 carbon atoms. Group, C 2 -C 12 alkylidene group, represents a benzylidene group, p- xylylene or cycloalkylidene group, and T is -SO -, -
SO _2- , -SO-E-SO-, -SO ₂ -E-SO ₂
-, -CO-, -CO-E-CO-, -COO-EO
CO— or —CO—NG ₅ —E-NG ₅ —CO— (wherein E is an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or a cycloalkylene group having 8 to 12 carbon atoms) or which is interrupted by cyclohexylene it represents an alkylene group-terminated groups, G ₅
Represents G ₃ or hydrogen atom. Where G ₂ is E
₃ SO- or E ₃ SO ₂ - if it is in, E ₁ is provided that is not a phenyl group. Compound represented by｝. 13. A compound of the formula I ′ (Wherein G ₂ is a cyano group, E ₃ SO ₂ —, CF ₃ —, —COO—
G ₃ —CO—NHG ₃ or —CO—N (G ₃ ) ₂ ;
G ₃ represents an alkyl group having 1 to 12 carbon atoms;
₁ is a hydrogen atom, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or the above-mentioned phenyl group or phenylalkyl group in which the phenyl ring is substituted by one or two alkyl groups having 1 to 4 carbon atoms. It represents; E ₂ is alkyl of 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group or a -CH of 7 to 15 carbon atoms
₂ CH ₂ COOG ₄ wherein G ₄ is substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, interrupted by 1 to 6 —O— atoms, or Substituted and 1 to 6
And E ₃ represents an alkyl group having 8 to 18 carbon atoms, an alkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms or 1 to 4 carbon atoms. Represents an aryl group as described above substituted by one or two alkyl groups; and G ₂ represents E ₃ SO
- or E ₃ SO ₂ - if it is in, E ₁ is provided that is not a phenyl group. 13. The compound according to claim 12, which is a compound represented by the formula: 14. In the formula I ′, G ₂ is a cyano group, E ₃ SO ₂ —, CF ₃ —, —COO—
G ₃ or -CO-N (G _{3) 2} a represents; G ₃ represents an alkyl group of 1 to 8 carbon atoms; E ₁ is hydrogen atom, a phenyl group or an α- cumyl; E ₂ carbon E ₃ represents an alkyl group having 4 to 12 atoms and E ₃ represents a phenyl group or an octyl group, provided that G ₂ is E ₃ SO ₂
- If it is the E ₁ is 13. A compound according to conditions that it is not α- cumyl. 15. Formula I 'wherein G ₂ represents CF _3- ; E ₁ represents an α-cumyl group or a phenyl group; and E ₂ represents a tert-butyl group or te.
15. The compound according to claim 14, which represents an rt-octyl group. 16. A compound according to claim 12, wherein (a) an organic material which is subject to heat, oxidation or light induced decomposition, and (b) a compound of the formula I according to claim 12,
A composition stabilized against heat, oxidation or light induced decomposition comprising an effective stabilizing amount of a compound represented by II, III or IV. 17. The composition according to claim 16, wherein the organic material is a natural, semi-synthetic or synthetic polymer. 18. The composition according to claim 17, wherein the polymer is a thermoplastic polymer. 19. The composition according to claim 18, wherein the polymer is a polyolefin or a polycarbonate. 20. The composition according to claim 19, wherein the polymer is polyethylene or polypropylene. 21. The composition according to claim 20, wherein the polymer is polypropylene. 22. An organic material wherein the organic material is a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin having a carbamate side group crosslinked with melamine, or an acrylic crosslinked with melamine containing a carbamate group. 17. The composition according to claim 16, which is a resin selected from the group consisting of polyol resins. 23. The composition according to claim 22, wherein the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin. 24. The composition according to claim 16, wherein the organic material (a) is a recording material. 25. A thermosetting acrylic melamine resin, acrylic urethane resin, epoxy carboxy resin, silane-modified acrylic melamine, acrylic resin having a carbamate side group crosslinked with melamine, or acrylic polyol resin crosslinked with melamine containing a carbamate group. 2. A composition according to claim 1, wherein the amount is from 0.01 to 5% by weight of resin solids for stabilizing a coating composition comprising a resin selected from the group. Using a benzotriazole compound.