JP2002518487A - Benzo ring-substituted triazine and pyrimidine ultraviolet absorbers - Google Patents

Abstract

  (57) [Summary] The present invention relates generally to benzo-ring-substituted pyrimidines and triazines and their use to protect against degradation by the effects of the environment, including ultraviolet light, actinic radiation, oxygen, moisture, air pollutants and combinations thereof. This new class of benzo-ring-substituted pyrimidines and triazines is characterized in that the benzo ring attached to the triazine or pyrimidine ring and, preferably, the hydroxyl group which is free or blocked to form a potential stabilizer, is added to the triazine or pyrimidine ring. It comprises an additional aryl ring which is ortho to the attached position. These materials bind, under appropriate circumstances, to a formulation comprising a coating, a primer, a polymer, a resin, an organic compound, and the like, by reaction with the materials of the formulation of the conjugated functional group. Methods for stabilizing materials by including such benzo-substituted pyrimidines and triazines are also disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to novel benzo ring-substituted pyrimidines and triazines and the effects of the environment including ultraviolet light, actinic radiation, oxygen, moisture, air pollutants and combinations thereof. To the use of these as inhibitors against degradation by.

2. Description of the Related Art Exposure to sunlight and other ultraviolet sources is known to cause degradation of various materials, especially polymeric materials. For example, polymeric materials such as plastics may become discolored or brittle as a result of exposure to ultraviolet light. Accordingly, many techniques have been developed for materials such as ultraviolet absorbers and stabilizers that can suppress such decomposition.

A class of materials known as UV absorbers are phenyl groups in which at least one substituent of one, three or five carbons on the triazine ring has a hydroxyl group ortho to the point of attachment of the triazine ring. , O-hydroxyphenyltriazine.
Generally, such materials are known in the art.

For example, US Pat. No. 3,843,371 discloses hydroxyphenyltriazines for photographic materials. However, the triazines of this patent show poor solubility and poor stability.

[0005] US Patent No. 3,896,125 discloses hydroxyphenyltriazines, which also have poor solubility and discolor over time.

[0006] Hydroxyphenyltriazine alone or hydroxyphenylbenzotriazole, benzophenone, oxanilide, cyanoacrylate, salicylate,
It is also known to use in combination with other light stabilizers such as hindered amine light stabilizers (HALS) to stabilize polymers. For example, U.S. Pat.Nos. 4,853,471 and 4,9
Nos. 21,966, and 4,973,701, 4,973,702 disclose such combinations.

[0007] Typically, the aforementioned aryl ring having an ortho hydroxyl group at the point of attachment to the triazine ring is based on resorcinol, so that the aryl ring also has a para-secondary position at the point of attachment to the triazine ring. Contains substituents (hydroxyl groups or derivatives thereof). For example, U.S. Pat. It shows poor compatibility and solubility and poor yellowing performance.

The para substituent may be “non-reactive,” as in the case of an alkyloxy group, or it may be a hydroxyalkyloxy group (active hydrogen reactive site) or (meth) acryloyl (ethylenically unsaturated group reaction). It can be "reactive" as in the case of a (site) group. For the purposes of the present invention, the former is referred to as "unbound" benzo-ring-substituted pyrimidines and triazines, and the latter is referred to as "bound" benzo-ring-substituted pyrimidines and triazines.

[0009] Low volatility is an important property of stabilizers used in applications subject to high temperatures. High temperatures are used for processing thermoplastics and curing thermosetting resins and coatings. Also, in the end use of stabilized materials, high temperatures are often present. Low volatility prevents loss of stabilizer during processing, curing and end use at elevated temperatures.
In addition to reducing stabilizer loss during processing or curing, low volatility minimizes processing problems such as lip build-up and plate-out.

[0010] Many polymer additives (such as UV stabilizers) migrate from the polymer substrate to be protected or can be replaced by one or more system components (such as pigments).
Adsorbed (chemically or physically), reducing its effectiveness. Such migration and adsorption problems are an example of the general problem of poor solubility and compatibility found in many commercial polymer additives.

[0011] Bound triazines are known in the art. For example, U.S. Pat.No. 3,423,360,
Nos. 4,962,142 and 5,189,084 disclose the incorporation of these compounds into polymers by chemical bonding with various linked triazines. The binding stabilizer is
Depending on the attached functional groups and the particular polymer system to be stabilized, either at the time of polymer formation (in the case of polymerization of monomers or crosslinking of the polymer system) or after
By reacting with a pre-formed polymer having suitable reactive functional groups at the attached functional group, there is a potential advantage in that the stabilizer can be chemically included in the polymer structure. Thus, such binding greatly reduces the migration of such UV absorbers between the layers of the multilayer coating or into the polymer substrate.

(Summary of the Invention) The present invention relates to the following, wherein the substituent attached to the triazine or the pyrimidine is

[0013]

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Wherein X represents hydrogen or a blocking group, A can be nitrogen or optionally substituted methine, and the fused ring represented by S contains one or more heteroatoms Optionally containing non-aromatic 4- to 12-membered rings, wherein any of the three rings may contain one or more additional substituents). I do.

[0015] These fused benzo ring-substituted triazines and pyrimidines have extremely high solubility and compatibility, have extremely low volatility, and therefore have low loss during high-temperature processing or curing, and are extremely effective in suppressing yellowing. And has the advantage of being extremely effective in preventing the decomposition of polymers and coatings by the action of actinic radiation, heat, oxygen and moisture.

The benzo ring-substituted pyrimidine and triazine UV absorbers of the present invention have an exceptionally low volatility, even lower than most UV absorbers of the state of the art. In addition, benzocyclic triazine UV absorbers impart improved weatherability and yellowing resistance to polymers compared to state of the art UV absorbers. The previously marketed triazine UV stabilizers and absorbers, combined with the weatherability, yellowing resistance, solubility and compatibility of the benzo ring-substituted triazine and pyrimidine UV absorbers and stabilizers of the present invention, are unexpected. Nothing has low volatility.

More specifically, the novel benzo ring-substituted pyrimidines and triazines of the present invention are
General formula (I)

[0018]

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Wherein each A is independently nitrogen or methine optionally substituted by R ² , and at least two A are nitrogen; each of T and T ′ is independently a direct bond; Carbon, oxygen, nitrogen, sulfur, phosphorus, boron,
Silicon or a functional group containing these elements, X is selected from hydrogen and a blocking group independently, R ^l and each R ² is independently a hydrocarbyl group, functional hydrocarbyl group, hydroxy, alkoxy, hydrogen, H, Z, R ³ and R ⁴ are each independently hydrogen, a hydrocarbyl group, a functional hydrocarbyl group, halogen, hydroxyl, cyano, -O (hydrocarbyl), -O (functional Hydrocarbyl), -N (hydrocarbyl) (hydrocarbyl), -N (functional hydrocarbyl)
) (Functional hydrocarbyl), - N (hydrocarbyl) (functional hydrocarbyl), - S (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (hydrocarbyl), - SO ₂ (hydrocarbyl), - SO ₃ ( hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO (hydrocarbyl), - COO (functional hydrocarbyl), - CO (hydrocarbyl), - CO (functional hydrocarbyl, --OCO (hydrocarbyl), - OCO (functional hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - CONH _2, -CONH (hydrocarbyl), - CONH (functional hydrocarbyl), - CON (hydrocarbyl) (hydrocarbyl), - CON (hydrocarbyl) (functional hydrocarbyl), -CON (functional hydrocarbyl) (functional hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl) -COO (functional hydrocarbyl), - CO (functional Hydro Ascorbyl), -
OCO (functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups, wherein each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorus, boron, silicon, selenium,
Tellurium, or a functional group containing these elements, each of m, n, and o is independently an integer between 0 and 4 (however, when both G are a direct bond, m, n And o is between 2 and 10, and if one G is a direct bond, the sum of m, n and o is between 1 and 9; if none of the G is a direct bond, Is the sum of m, n and o between 0 and 8), p is an integer between 0 and 3, and q is an integer between 0 and 20).

Preferably, T ′ is an oxygen atom, Y is a group L and has the formula (II)

[0021]

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Wherein L is as defined for Y, Z, R ³ and R ⁴ as defined above, and the substituents A, G, T, X, Y, Z, R ¹ to R ⁴ , And subscripts m, n, o, p, and q are represented by the general formula (1)
Benzo-ring-substituted pyrimidines and triazines derived from mono-resorcinol are defined above.

More preferably, TZ in formula (II) is represented by formula (IIla) or (IIlb)

[0024]

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A resorcinol derivative of the formula (IVa) and (IVb)

[0026]

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A triazine derived from a monobenzocyclic bis-resorcinol is obtained.

More preferably, each L in Formulas III and IV is independently hydrogen; optionally substituted by one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amide, carbamate, or epoxy groups Alkyl of 1 to 24 carbon atoms, which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino Alkenyl of 2 to 24 carbon atoms, optionally substituted by amide, carbamate, or epoxy groups, and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain; More hydroxy, alkoxy, chloro, cyano, carbo 7 to 24 carbon atoms optionally substituted by a xy, carboalkoxy, amino, amide, carbamate or epoxy group and which may contain one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain aralkyl; formula _{XII -CH 2 -CH (OH) -CH} 2 -O- (CH 2 - (CH 2) u -O-) mm -D 1 (XII) ( wherein, D _l is hydrogen, -CH ₂ -CH (OH) -CH ₂ -OH,

[0029]

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Or a R ²⁵ ) polyoxyalkylene group of the formula: XIII—CO— (CH ₂ ) _u —O— (CH ₂ — (CH ₂ ) _u —O—) _mm —D ₂ (XIII) Wherein D ₂ is-(CH ₂ ) -CO-R ²² or R ²⁵ ); a polyoxyalkylene group of the formula VIII -YY-O-CO- (CH ₂ ) _u -O- (CH _2- (CH _{2) u -O-) mm -D 3} (XIV) ( wherein, D ³ is _{- (CH 2) u -CO-} R 22 or R ²⁵⁾ of the polyoxyalkylene group; formula XV - (CH ₂ ) _kk -CH (R ²¹ ) -CO-B _1- (C _nn H _2nn -O-) _mm -C _nn H _2nn -B ₁ -D ₄ (XV) (where D ₄ is hydrogen or R ²⁵ polyoxyalkylene groups present); wherein _{XVI -CO-CH 2 -CH 2 -NH-} (C nn H 2nn -O-) mm -C nn H 2nn -D 5 (XVI) ( wherein, D ₅ is - NH ₂ , —NH— (CH ₂ ) ₂ —COO—R ²³ or —OR ²⁵ ), a formula XVII—YY—O—CO—CH ₂ —CH ₂ —NH— (C _nn H _2nn -O-) _mm -C _nn H _2nn -D ₅ (XVII), wherein D ₅ is as defined under formula (XVI), of the formula _XVIII- (C _nn H _2nn -O-) _mm A polyoxyalkylene group of -C _nn H _2nn -D ₆ (XVIII), wherein D ₆ is -NH-CO-R ²⁴ , -OR ²⁵ , OH or H;

[0031]

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Wherein D ₇ is —OR ²⁵ , —NHCOR ²⁴ or —OCH ₂ CH ₂ OR ²⁵ , wherein R ²¹ is hydrogen or C ₁ -C ₁₆ alkyl; R ²² is halogen or -OR ²³ ; R ²³ is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, aryl, or aryl-C _1-
C ₄ - alkyl, R ²⁴ is hydrogen, C ₁ -C ₁₂ alkyl or aryl, R ²⁵ is C ₁ -C ₁₆ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C was ₁₂ alkyl or aryl C _l -C ₄ alkyl, R ²⁶ is hydrogen or C _l -C ₄ alkyl, R ²⁷ is hydrogen, C _l ^- C ₁₈ alkyl, C ₃ -C ₆ alkenyl, Cl ^- C ₁₈ alkoxy, halogen or aryl -C _l ^- C ₄ ^- alkyl, independently hydrogen R ²⁸ and R ²⁹ to each other, C _l -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C _l -C ₁₈ alkoxy, or halogen,, R ³⁰ is hydrogen, C _l -C ₄ alkyl or CN, YY is unsubstituted or substituted C ₂ -C ₂₀ alkyl, kk is an integer of zero or 1 -1 6 , B _l is O or NH, mm is an integer from 2 to 60, nn is an integer from 2 to 6, and u is an integer from 1 to 4.

Preferred in the present invention are compounds of formula (IV) wherein both G are direct bonds, m = 4, n, o, p and q are 0, and all A are of formula (IVc )

[0034]

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Is a compound of the formula

Further preferred in the present invention is a compound represented by the formula (V)

[0037]

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Wherein the substituents are as defined above for general formulas (I) to (IV), bis-benzo ring substituted pyrimidines and triazines.

Most preferred in the present invention are compounds of formula 5 wherein all G are direct bonds, m = 4; n, o, p and q are 0, and all A are nitrogen Wherein the compound has the formula

[0040]

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Wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or 1 to 24
X is independently selected from hydrogen and a blocking group; R ³ and R ⁴ are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), -O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl), - COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO (Functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano).

The benzo-ring-substituted pyrimidines and triazines of the present invention may further comprise a compound of the formula (VI) or (VII)

[0043]

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(Where A, T, T ′, Y, Z, R^l-R^Four, G, m-q, and X are as defined above.
Where r is an integer between 2 and 4, and if r is 2, D is C_Two-C₁₆ Alkyl, C_Four-C₁₂ Alkenyl, xylylene
, C interrupted by one or more oxygen atoms_Three-C₂₀Alkyl, there is one
Or a hydroxy-substituted C interrupted by more oxygen atoms_Three-C₂₀Alkyl, -CH _Two CH (OH) CH_TwoO-R¹⁵-OCH_TwoCH (OH) CH_Two, -CO-R¹⁶CO-, -CO-NH-R¹⁷-NH-CO-,-(CH_Two)_s-CO
O-R¹⁸-0CO- (CH_Two)_s, The formula XX -CH_Two-CH (OH) -CH_Two-O- (CH_Two-(CH_Two)_u-O-)_mm-CH_Two-CH (OH) -CH_Two-A polyoxyalkylene bridging member of (XX), of the formula XXI -CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-(CH_Two)_u-CO- (XXl), a polyoxyalkylene bridging member of the formula XXII -YY-O-CO (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-(CH_Two)_u-COO-YY- (XXII), a polyoxyalkylene bridging member of the formula XXIII-(CH_Two)_kk-CH (R^{twenty one}) CO-B₁-(C_nn-H_2nn-O-)_mm-C_nnH_2nn-B₁-CO-CH (R^{twenty one})-(CH_Two)_kk-A polyoxyalkylene bridge member of (XXIll), of the formula XXIV

[0045]

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A polyoxyalkylene bridging member of the formula XXV-YY-O-CO- (CH ₂ ) ₂ -NH- (C _nn H _2nn -O-) _mm -C _nn H _2nn -NH- (CH ₂ ) ₂ COO-YY-polyoxyalkylene bridge member of (XXV), wherein _{XXVI - (C nn H 2nn -O-} ) mm -C nn H 2nn - polyoxyalkylene bridge member of (XXVI), and the formula XXVII -CH (CH ₃ ) -CH _2- (O-CH (CH ₃ ) -CH ₂ ) _a- (O-CH ₂ -CH ₂ ) _b- (O-CH ₂ -CH (CH ₃ ) _c- (XXVII) , A + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0
R ²¹ is hydrogen or C ₁ -C ₁₆ alkyl, R ²² is halogen or —OR ²³ , R ²³ is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, aryl, or aryl-C _1-
C ₄ - alkyl, R ²⁴ is hydrogen, C ₁ -C ₁₂ alkyl or aryl, R ²⁵ is C _l -C ₁₆ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₂ alkylaryl or aryl-C ₁ -C ₄ alkyl, R ²⁶ is hydrogen or C ₁ -C ₄ alkyl, R ²⁷ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₈ alkoxy, halogen or aryl-C ₁ -C ₄ alkyl, wherein R ²⁸ and R ²⁹ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, or C _1- C _l8 alkoxy or halogen,, R ³⁰ is hydrogen, C ₁ -C ₄ alkyl or CN, YY is unsubstituted or substituted C ₂ -C ₂₀ alkyl, kk is zero or 1 - 1 6 integer Where B _l is 0 or NH, mm is an integer from 2 to 60, nn is an integer from 2 to 6, u is an integer from 1 to 4, and if r is 3, , D is

[0047]

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If r is 4, D is

[0049]

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(Wherein R ¹⁹ is C ₃ -C _{10 alkantotril} , R ²⁰ is C ₄ -C _{10 alkantetrile} , s is 1-6
And R ¹⁵ is C ₂ -C ₁₀ alkyl, C ₂ -C ₁₀ oxoalkyl or C ₂ -C ₁₀ dithioalkyl, phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl, or phenylene-X
X- phenylene (wherein, XX is _{-O-, -S-, -SO 2 -,} - CH 2 - or -C (CH _{3) 2} - a is)
Wherein R ¹⁶ is C ₂ -C ₁₀ alkyl, C ₂ -C ₁₀ oxoalkyl or C ₂ -C ₁₀ dithioalkyl, phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl (where r is 3) Wherein alkenyl has at least 3 carbons), and R ¹⁷ is C ₂ -C ₁₀ alkyl, phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl, methylenediphenylene, or C ₄ -C ₁₅ alkyl phenyl, also R ¹⁸ is an oligomer species is C ₂ -C ₁₀ alkyl, or one or C ₄ -C ₂₀ alkyl which is interrupted by more oxygen atoms)

[0051]

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Wherein A, T, T ′, Y, Z, R ¹ -R ⁴ , G, mq, and X are as defined above, r is 2 or 3, and r is If it is 2, X 'is ^{-CO-R 16 -CO -, -} C0 2 -R 16 -CO 2 -, - SO 2 -R 16 -SO 2 -, - CO-N
HR ¹⁷ -NH-CO-, -CO- (CH ₂ ) _u -O- (CH _2- (CH ₂ ) _u -O-) _mm- (CH ₂ ) _u -CO-, a polyoxyalkylene bridge member, or

[0053]

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And when r is 3, X ′ is-(-CO ₂ -R ¹⁶ ) R ¹⁹ ,-(-CONH-R ¹⁶ ) R ¹⁹ ,-(-SO ₂ -R ¹⁶ ) R ^{19 (wherein, R 16, R l7, R} l8, and R ¹⁹ is as defined above) comprising the oligomeric species are).

The benzo-ring-substituted pyrimidines and triazines of the present invention also have the formula (VIII) and (IX)

[0056]

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Wherein A, T, T ′, Y, Z, R ¹ to R ³ , G, m to q, and X are as defined above, and R ⁴ is 1 to 12 Straight-chain alkyl of carbon atoms, branched alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, substituted by phenylene Alkyl, phenylene interrupted alkyl, benzylidene, -S-
, -SS-, -SES-, -SO -, - SO 2 -, - SO-E-SO -, - SO 2 -E-SO 2 -, CH 2 -NH-E-NH-CH 2 - and

[0058]

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Wherein E is alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, 8 to 12 alkyl interrupted by cyclohexyl, and cyclohexyl terminated 8 Is an alkyl of 12 carbon atoms from), and r is an integer between 2 and 4.)

[0060]

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Wherein each A is independently nitrogen or methine optionally substituted by R ² , and at least two A are nitrogen; each of T and T ′ is independently a direct bond; Carbon, oxygen, nitrogen, sulfur, phosphorus, boron,
Silicon, or a functional group containing these elements, each of Y, Z, R ¹ , and R ² is independently a hydrocarbyl group, a functional hydrocarbyl group,
Hydrogen, halogen, cyano, or isocyano; each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorus, boron, silicon, selenium,
Tellurium, or a functional group containing these elements, each of m, n, and o is independently an integer between 0 and 4 (however, when both G are a direct bond, m, n And the sum of o is between 2 and 10, and if one G is a direct bond, the sum of m, n and o is between 1 and 9, and if no G is a direct bond, Is the sum of m, n and o is between O and 8), p is an integer between 0 and 3, q is an integer between 0 and 20, X is independently hydrogen or a blocking group, R ³ and R ⁴ are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), - O (functional hydrocarbyl), - S (hydrocarbyl), - SO ₂ ( hydrocarbyl), - SO ₃ (hydrocarbyl), - COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO (Functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano, where r is an integer between 2 and 4 , When r is 2, D is C ₂ -C ₁₆ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, C ₃ -C ₂₀ alkylene interrupted by one or more oxygen atoms, one or more oxygen hydroxy-substituted C ₃ -C ₂₀ alkylene which is interrupted by ^{atom, -OOC-R 14 -COO -,} - CH 2 CH (OH) CH 2 oR 15 -OCH 2 CH (OH) CH 2, -CO ^{-R 16 CO -, - CO-} NH-R 1 7 -NH-CO-, and _{- (CH 2) s -COO-} R 18 -OCO- (CH 2) selected from the group consisting of _s, r is 3 Place that is The, D is,

[0062]

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When r is 4, D is

[0064]

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Wherein R ¹⁹ is C ₃ -C _{10 alkanthryl} , R ²⁰ is C ₄ -C _{10 alkantetrile} ,
s is 1-6), r is an integer between 2 and 4, and when r is 2, D is C ₂ -C ₁₆ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, one or interrupted by more oxygen atoms C ₃ -C ₂₀ alkylene, one or more oxygen hydroxy-substituted C ₃ -C ₂₀ alkylene which is interrupted by _{atom, -CH 2 CH (OH) CH} 2 oR ¹⁵ -OCH ₂ CH (OH) CH ₂ , -CO-R ¹⁶ CO-, -CO-NH-R ¹⁷ -NH-CO-, and-
Is selected from the group consisting of (CH ₂ ) _s -COO-R ¹⁸ -OCO- (CH ₂ ) _s-, and when r is 3, D is

[0066]

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When r is 4, D is

[0068]

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Where R¹⁹Is C_Three-C_l0Alcantril, R²⁰Is C_Four-C_l0Alkantetrile,
s is 1-6) and R⁸Is C_l-C₁₈ Alkyl, C_Three-C₁₈Interrupted by alkenyl, O, N or S, and
And / or C substituted by OH_Three-C₂₀Alkyl, -P (O) (OR¹⁴)_Two, -N (R⁹) (Rl0),
Or -OCOR^1lAnd / or C substituted by OH₁-C_Four Is an alkyl
Or glycidyl, cyclohexyl or C₇-C₁₁Phenylalkyl; R⁹And R^TenAre each independently of the other_l-C_l2Alkyl, C_Three-C₁₂Alkoxyalkyl, C _Four -C₁₆Dialkylaminoalkyl or C_Five-C₁₂Cycloalkyl, or together
Then R⁹And R^l0Is C_Three-C₉ Alkylene, C_Three-C₉Oxaalkylene or C_Three-C₉A
Zalkylene and R^l1Is C_l-C₁₈Alkyl, C_Two-C₁₈Alkenyl or phenyl; R¹²Is C_l ^-C₁₈Alkyl, C_Two-C₁₈ Alkenyl, phenyl, C_l-C₁₂Alkoxy, Fe
Noxy, C_l ^-C₁₂Alkylamino, phenylamino, tolylamino or naphthyl
Amino and R¹³Is C_l-C₁₂Alkyl, phenyl, naphthyl or C₇-C₁₄Alkylphenyl
R¹⁴Is C₁-C₁₂Alkyl or phenyl; R¹⁵Is C_Two-C_l0Alkylene phenylene or phenylene-X-phenylene group (wherein X
Is -O-, -S-, -SO_Two-, -CH_Two-Or -C (CH_Three)_Two-Is) and R¹⁶Is C_Two-C_l0Alkyl, C_Two-C_l0Oxoalkyl or C_Two-C_l0Dithioalkyl,
Phenylene, naphthylene, diphenylene, or C_Two-C₆ Alkenylene and R¹⁷Is C_Two-C_TenAlkylene, phenylene, naphthylene, methylenediphenylene or
Is C₇-C₁₅ Alkylphenylene and R¹⁸ Is C_Two-C_TenInterrupted by alkylene or one or more oxygen atoms
C_Four-C₂₀ Which is an alkylene).

The benzo ring-substituted pyrimidine and triazine of the present invention may optionally have a functional group attached to the benzo ring, pyrimidine and triazine group (eg, R ¹ , R ² , Y or
The added advantage is the ability to chemically bond to suitable polymer systems via hydroxyl, ethylenically unsaturated groups and / or activated unsaturated groups in one or more of Z). .

These benzo ring-substituted pyrimidines and triazines are generally described, for example, by Brunet
ti, H; Luethi, C .; Helv. Chemica Acta, 55 (1972) 1566-1595; Tanimoto,
S .; Yamagata, M. Senryo to Yakuhin, 40 (1995) ₃ 39; U.S. Patent Nos. 5,106,972, 5,288,868, 5,
Nos. 438,138 and 5,478,935; EP 395,938; EP 577,559; EP 649,841; EP 7
79,280; WO 9,628,431; GB 884,802; and those described in Japanese Patent Publication No. 9,059,263.

The novel benzo-ring-substituted pyrimidines and triazines of the present invention include, for example, organic compounds, oils, fats, waxes, cosmetics, dyes and biocides, and especially photographic materials, plastics, fibers or dyed fibers, rubbers, paints It is particularly useful as a UV absorber for stabilizing a wide variety of materials, including various organic polymers (both cross-linked and non-cross-linked) used in applications such as and other coatings, and adhesives. As a result, the present invention also comprises a benzo ring-substituted 1,3,5-triazine and pyrimidine of the present invention, wherein the amount of actinic radiation is effective to stabilize the material against the effects of actinic radiation. A method of stabilizing a material that undergoes degradation by actinic radiation (eg, an organic material such as an organic polymer in the form of a film, fiber, molded article, or coating) by including a stabilizer composition in the material; and 2) It also relates to such stabilized materials.

The novel benzo ring-substituted pyrimidines and triazines of the present invention also include, inter alia,
It is useful as an UV cut agent in applications such as sunscreens and other cosmetic preparations, extruded polymer coatings, dyed fibers and laminated UV cut window films. As a result, the present invention also provides an actinic radiation-cutting composition comprising (1) an actinic radiation-cutting composition comprising a benzo ring-substituted pyrimidine and a triazine of the present invention in an amount effective to reduce the actinic dose applied to a substrate. It also relates to a method of applying a layer (eg a coating film or a coating layer) to a substrate to protect the substrate against degradation by actinic radiation, and (2) a material thus stabilized.

The novel benzo ring-substituted pyrimidines and triazines of the present invention can also be used to make light stabilizer compositions. Such light stabilizer compositions include other UV absorbers of the triazine class, different classes of UV absorbers (e.g., benzotriazole,
Benzophenone), hindered amine light stabilizers, radical scavengers, antioxidants and the like.

[0075] These and other features of the present invention will be more readily understood by those of ordinary skill in the art upon reading the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Benzo-Ring-Substituted Pyrimidines and Triazines As used herein, the term “benzo-ring-substituted pyrimidines and triazines” is broadly defined by the above formulas (1) through (1) IX). As used herein, the term "benzo ring" is broadly defined by the general formula (X)

[0077]

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(Wherein the substituents G, R ¹ , R ² and the subscripts m, n, o, p, and q are represented by the general formulas (1), (II)
), (III), and (IV) as defined above).

The term “hydrocarbyl” in the context of the present invention and in the above formula,
Broadly, it refers to a monovalent hydrocarbon group that produces a valence by abstraction of hydrogen from a carbon atom. Hydrocarbyls include, for example, aliphatic (linear and branched), cycloaliphatic, aromatic and mixed nature groups (eg, aralkyl and alkaryl). Hydrocarbyl also includes such groups with internal and activated unsaturation.
In particular, hydrocarbyl comprises groups such as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl, preferably having up to 24 carbon atoms. Hydrocarbyl optionally contains a carbonyl group (included in the carbon number) and / or a heteroatom (such as at least one oxygen, sulfur, nitrogen or silicon) in the chain or ring.

The term “functional hydrocarbyl” in the context of the present invention and in the above formula broadly comprises pendant and / or terminally reactive and / or latently reactive functional groups and / or leaving groups. Refers to hydrocarbyl. A "reactive" functional group
Refers to functional groups that are reactive with normal monomer / polymer functional groups under normal conditions that are well understood by those skilled in the relevant art. Non-limiting examples of reactive functional groups include hydroxyl, amino, carboxyl, thio, amide, carbamoyl and active methylene; isocyanato; cyano; epoxy; ethylenically unsaturated groups such as allyl and methallyl; and acryloyl and methacryloyl And active hydrogen-containing groups such as maleates and maleimides (including Diels-Alder adducts with dienes such as butadiene). A "latent reactive" functional group in the sense of the present invention refers to a reactive functional group that is blocked or masked to prevent premature reaction, as will be appreciated by those skilled in the relevant art. Examples of latent reactive functional groups include ketimines and aldimines (amines blocked by ketones and aldehydes, respectively); amine-carboxylate salts; and blocked isocyanates (carbamates) such as alcohols, blocked variations of oximes and caprolactam. Is mentioned. A "leaving" group in the sense of the present invention forms a valency at a carbon or heteroatom in a hydrocarbyl chain or ring by displacement or substitution during the reaction, as will be well understood by those skilled in the relevant art. A substituent on a hydrocarbyl chain or ring whose valency is filled by a nucleophile.
Examples of leaving groups include halogen atoms such as chlorine, bromine and iodine; hydroxyl groups
(Protonated and unprotonated); quaternary ammonium salt (NT ₄ ^+); sulfonium salt (ST ₃ ^+); and sulfonates (-OS0 ₃ T) (wherein, T is for example, methyl or para -
Tolyl). Of all the reactive functional groups of these classes, preferred functional groups are ^{hydroxyl, -COOR 5, -CR 6 = CH} 2, -CO-CR 6 = CH 2, Cl, an isocyanate group, blocked isocyanate groups And -NHR ⁵ wherein R ⁵ is selected from hydrogen and hydrocarbyl (preferably up to 24 carbon atoms), and R ⁶ is hydrogen and 1
To 4 carbon atoms (preferably selected from hydrogen and methyl).

The term “hydrocarbylene” in the context of the present invention is a divalent hydrocarbon radical in which abstraction of hydrogen from a carbon atom results in both valencies. Included within the definition of hydrocarbylene are the same groups indicated for hydrocarbyl and functional hydrocarbyl, of course, those with higher valences
(Eg, alkylene, alkenylene, arylene, alkylaryl, etc.).
The term "functional hydrocarbylene" in the context of the present invention refers to a species of hydrocarbylene having pendant reactive, potentially reactive functional groups and / or leaving groups. The term "non-functional hydrocarbylene" in the context of the present invention generally refers to a hydrocarbylene other than a functional hydrocarbylene.

The benzo-substituted pyrimidines and triazines according to the invention also have the general formula (1
), (III), and (IV) wherein at least one of the ortho hydroxyl groups at the point attached to the triazine or pyrimidine ring on the aryl ring is blocked, i.e., at least one X is other than hydrogen A) a potential stabilizing compound for actinic radiation. Such a potential stabilizing compound, by cleavage of the OX bond,
For example, heating or exposure to UV light releases the effective stabilizer. Potentially stabilizing compounds are desirable because they have a number of favorable properties: good substrate compatibility, good color, high OX bond cleavage rate and long shelf life. The use of potential stabilizing compounds is disclosed in U.S. Patent Nos.
No. 54 further describes this.

A potentially stabilizing compound comprising a benzo-ring-substituted pyrimidine and a triazine according to the present invention is subjected to further reaction of said compound, as described in the immediately incorporated citation, By producing a stabilizing compound, general formula (I),
It can be prepared from compounds of (IX) (II) and (IV) wherein at least one X is hydrogen.

Preferred examples of the blocking group X include one or more of the following groups. _{^{Allyl, -COR a, -S0 2 R b}} , -SiR c R d R e, -PR f R g or -POR ^f R ^g, -CONHR ^h (
Wherein each R ^a is independently C ₁ -C ₈ alkyl, halogen-substituted C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₈ alkenyl, -CH ₂ -CO-CH ₃ , C ₁ -C ₁₂ alkoxy, and phenoxy or phenyl unsubstituted or substituted by C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, halogen and / or benzyl, wherein each R ^b is independently C _1- C ₁₂ alkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₈ alkyl aryl, wherein each R ^c , R ^d and R ^e is independently C ₁ -C ₁₈ alkyl, cyclohexyl, phenyl and
C _l -C _l8 selected from alkoxy, each R ^f and R ^g are independently C _l -C ₁₂ alkoxy, C _l -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, and unsubstituted or C _l - Selected from C ₁₂ alkyl, C ₁ -C ₄ alkoxy, phenyl or phenoxy substituted by halogen and / or benzyl, and each ^Rh is independently C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, ₂ -C ₈ alkenyl, -CH ₂ -CO-CH _3, and unsubstituted or C _l -C ₁₂ alkyl, C ₂ -C ₈ alkenyl, C _l -C ₄ alkoxy, substituted by halogen and / or benzyl Selected from phenyl).

Potential stabilizing compounds of the invention of the general formulas (I), (III) and (IV), wherein X is allyl, —COR ^a , —SO ₂ R ^b , —SiR ^c R ^d The reaction for obtaining R ^e , -PR ^f R ^g or -POR ^f R ^g , is, for example, a compound of the general formulas (III) to (X), wherein at least one X is allyl chloride, Cl-COR ^a , ^{_{Cl-S0 2 R b, Cl}} -SiR c R d R e, may be carried out by reaction of Cl-PR ^f R ^g, or the corresponding hydrogen with halides such as Cl-POR ^f R ^g). General formula (I
The reaction to obtain a potentially stabilized compound of the present invention from (II) to (X), wherein X is -CONH ^h , is, for example, a compound of the general formula (III) to (X) At least one X
Is hydrogen with the corresponding isocyanate). Furthermore,
As is known to those skilled in the art, acylated compounds can be obtained by reaction with an ester such as an anhydride, ketene or a lower alkyl ester. The above reagents are
They are used in approximately equimolar amounts or in excess, for example in the starting compounds of the general formulas (I), (III) or (IV) in 2 to 20 mol with respect to the hydroxyl groups which are desired to be latent.

The catalysts conventionally used in acylation, sulfonylation, phosphonylation, silylation or urethanation reactions are used to form the potentially stabilized benzo-substituted pyrimidines and triazines of the present invention. You. For example, acylation and sulfonylation reaction catalysts such as tertiary or quaternary amines such as triethylamine, dimethylaminopyridine or tetrabutylammonium salts are used to generate these potentially stabilizing compounds.

The reaction is carried out in the presence of a relatively inert organic material, for example a hydrocarbon such as toluene and xylene, a chlorinated hydrocarbon such as carbon tetrachloride or chloroform, or a solvent such as an ether such as tetrahydrofuran or dibutyl ether. Or without solvent. Alternatively, the reagent is used as a solvent. The reaction temperature is usually between room temperature and about 150 ° C., for example, up to the boiling point of the solvent when a solvent is used.

In a preferred embodiment, each X is hydrogen.

In a preferred embodiment, L is hydrogen; C ₁ -C ₂₄ alkyl or a mixture thereof; C ₁ -C ₂₄ branched alkyl or a mixture thereof; C ₃ -C ₆ alkenyl; -COR ¹² ; _{^{COOR 12; -CONHR 12; -S0 2}} R 13; one or more radicals optionally substituted C _l -C ₁₈ alkyl: hydroxy, C ₁ -C ₁₈ alkoxy, C ₃ -C ₁₈ alkenoxy, halogen, phenoxy , C _l -C ₁₈ alkyl - substituted phenoxy, C ₁ -C ₁₈ alkoxy - substituted phenoxy, halogen - substituted _{^{phenoxy, -COOH, -COOR 8, -CONH 2}} , -CONHR 9, -CO
^{N (R 9) (R l0} ), - NH 2, -NHR 9, -N (R 9) (R 10), - NHCOR 11, -N (R 9) COR 11, NHCOOR 11,
-N (R ⁹ ) COOR ¹¹ , -CN, -OCOR ¹¹ , -OC (O) NHR ⁹ , -OC (O) NHR ⁹ , -OC (O) N (R ⁹ ) (R ¹⁰ ); Interrupted by further oxygen atoms or carbonyl groups, optionally hydroxy, C ₁ -C ₁₂ alkoxy, and glycidyloxy; glycidyl;
And optionally C ₂ -C ₅₀ alkyl substituted by one or more substituents selected from hydroxyl or cyclohexyl substituted by -OCOR ¹¹ , wherein R ⁹ and R ¹⁰ are independent of each other C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkoxyalkyl, C ₄ -C ₁₆ dialkylaminoalkyl, or C ₅ -C ₁₂ cycloalkyl, or R ⁹ and R ¹⁰ when taken together are C ₃ -C ₉ alkylene or C ₃ -C ₉ oxaalkylene or C ₃ -C ₉ azaalkylene, and R ¹¹ is C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or phenyl.

Some of these groups, as well as others, are incorporated herein by reference for all purposes, US Pat. No. 5,106,891, US Pat. No. 5,189,084, US Pat. No. 5,356,995.
No. 5, U.S. Patent No. 5,637,706, U.S. Patent No. 5,726,309, EP 434,608, EP 704,
437, WO 96/28431, and GB 2,293,823.

L is also an alkyl of 1 to 24 carbon atoms substituted by a hindered amine light stabilizer (HALS) group of general formula XI. Triazines containing a tetramethylpiperidine group are disclosed in U.S. Pat.
No. 5,376,710.

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(Wherein J is -O-, -NR ^30- , -T- (CH ₂ ) ₂ -NR ^30- (where T is -O- or -S-, and R ³⁰ is
C a _l -C a ₁₂ alkyl or hydrogen), R ³¹ is hydrogen or C _l -C ₈ alkyl, R ³² is hydrogen, oxygen, C _l -C ₂₁ alkoxyalkyl, C ₇ -C ₈ aralkyl, 2,3-epoxypropyl, and 1-4 C atoms or -CH ₂ COOR ³³ , -O-CH ₂ -CH (R ³⁴ ) -OR ³⁵ , -COO
R ³⁶ or one of the groups of -CONHR ³⁶ , wherein R ³³ is C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl, R ³⁴ is hydrogen, Methyl or phenyl; R ³⁵ is hydrogen, aliphatic, aromatic, arylaliphatic or an acyclic acyl group of 1 -8 C atoms, wherein the aromatic moiety is unsubstituted or chlorine, C ₁ C ₄ alkyl, by C ₁ -C ₈ alkoxy, or substituted by hydroxyl, R ³⁶ is C _l ^- a C ₁₂ alkyl, aliphatic acyl groups having a cyclohexyl, phenyl or benzyl)), R ³⁷ is hydrogen, —OH or —O—CO—R ³⁸ or one of the —NR ³⁶ —CO—R ³⁸ groups, where R ³⁸ is
C ₁ -C ₁₂ alkyl or phenyl), and K is -O- (C _mm H _2mm )-, where mm is 1 to 6.

Preferred among the sterically hindered amines are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis (1,2,2,6,6-pentamethylpiperidine-4 -Yl) sebacate, bis (1-octyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
N, N'-bis (2 2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine
Condensation product of 4-t-octylamino-2,6-dichloro-1,3,5-triazine, N, N′-bis (2,
Condensate of 2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 3-dodecyl 1- (2,2,6 , 6-Tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 3-dodecyl 1- (1-acetyl
-2 2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine And mixtures thereof.

Most preferably, each L group is independently hydrogen, alkyl of 1 to 24 carbon atoms,
Or mixtures thereof; 4 to 2 containing one or more oxygen atoms in the chain, optionally substituted by one or more hydroxyl groups
Alkyl of 0 carbon atoms, or a mixture thereof.

Each R ¹ and R ² is independently hydrogen, chloro, alkyl of 1 to 8 carbon atoms, alkyloxy of a group of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain,
Oxygen atoms, optionally containing 1 to 8 carbon atoms in the chain, alkyloxy of 1 to 8 carbon atoms, optionally containing 1 to 8 oxygen atoms in the chain Selected from the group consisting of hydroxyalkyloxy, a group of 2 to 12 carbon atoms, and an acyloxy of 2 to 12 carbon atoms. Particularly preferred is that each R ¹ and R ² is independently selected from hydrogen, chloro, alkyl of 1 to 4 carbon atoms, and alkoxy of 1 to 4 carbon atoms, especially hydrogen, methyl, and methoxy Is the case.

Each R^ThreeAnd R^Four Is independently hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, 1
A hydrocarbyloxy group of 24 carbon atoms, an acyl group of 2 to 24 carbon atoms
And acyloxy groups of 2 to 24 carbon atoms. More preferably, each R ¹ Is independently 1 to 24 carbon atoms, optionally containing hydrogen and oxygen atoms in the chain
Alkyl, alkyl of 1 to 24 carbon atoms, optionally with oxygen atoms in the chain
Alkoxy, an alkyl of 2 to 24 carbon atoms optionally containing oxygen atoms in the chain
Nyl, alkenyl of 2 to 24 carbon atoms optionally containing an oxygen atom in the chain
Oxy, acyl groups of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms
It is selected from groups and optionally substituted benzoyl. Still more preferably
, Each R¹Is independently hydrogen, alkyl of 1 to 8 carbon atoms, oxygen atom in the chain
Depending on alkyloxy of 1 to 8 carbon atoms, if oxygen atom in the chain
Some contain 1 to 8 carbon atoms, including hydroxyalkyl and oxygen atoms in the chain.
May contain 1 to 8 hydroxyalkyloxy of 1 to 8 carbon atoms, 2 to 12
And acyloxy of 2 to 12 carbon atoms.
Some of these groups, as well as others, are incorporated herein by reference for all purposes.
U.S. Patent No. 5,189,084; U.S. Patent No. 5,354,794; U.S. Patent
No. 5,543,518, U.S. Pat.No. 5,637,706, EP 434,608, EP 704,437, and WO 9
6/28431.

In a preferred embodiment, each R ³ and R ⁴ is independently hydrogen, halogen, acyl of 2 to 24 carbon atoms, benzoyl, alkyl of 1 to 24 carbon atoms, 2 to 24
Alkenyl of 5 carbon atoms, cycloalkyl of 5 to 24 carbon atoms and 7 to 2
Selected from aralkyl of 4 carbon atoms.

In another preferred embodiment, R ³ and R ⁴ are independently methylene, alkylidene, or benzylidene substituted with a benzophenone or benzotriazole UV absorber. Related triazine-benzotriazole and triazine-benzophenone hybrid UV absorbers are described in US Pat. No. 5,585,422, which is incorporated herein by reference for all purposes. In a related preferred embodiment, R ³ and R ⁴ are independently methylene, alkylidene, or benzylidene substituted with a second triazine UV absorber. Related triazine dimers (and oligomers) are described in US Pat. No. 5,726,309 and EP 704,437, which are hereby incorporated by reference for all purposes.

Preferred benzotriazoles are 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole; 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole; 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole; 2- (
2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole; 2- (3', 5'-di-t-butyl-2'-hydroxyphenyl) -5- Chlorobenzotriazole; 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole; 2- (3'-s-butyl-5'-t-butyl- 2'-hydroxyphenyl) -benzotriazole; 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole; 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzo Triazole; 2- (3
', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole; 2- (3'-t-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl ) Phenyl) -5-chloro-benzotriazole, 2- (3′-t-butyl-5 ′-[2- (2-ethylhexyloxy) -carbonylethyl] -2′-hydroxyphenyl) -5-chloro-
Benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-2' -Hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t
-Butyl] -2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole and 2- (3'-t-butyl-5'-[2- (2-ethylhexyloxy) carbonylethyl] -2 '-Hydroxyphenyl) benzotriazole, 2- (3'-dodecyl]-
2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-t-butyl-2
Mixture of '-hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole; 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-
Benzotriazol-2-ylphenol], 2- [3'-t-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole transesterification product with polyethylene glycol 300; R-CH ₂ CH-COO (CH ₂ ) ₃ ] _2- (where R = 3′-
t-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl) and at least one member of the group consisting of these derivatives.

The most preferred benzotriazoles are 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole; 2- (3 ′, 5′-di-t -Amyl-2'-hydroxyphenyl) benzotriazole; 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole; 2- (3'-t-butyl -2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole,
2- [3'-t-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl]
It is a member of the group consisting of the transesterification products of benzotriazole with polyethylene glycol 300 and mixtures thereof.

In a preferred embodiment, R ^ll is optionally substituted by hydrogen and hydroxyl or alkoxy of 1 to 4 carbon atoms and / or comprises one or more oxygen and / or nitrogen atoms in the chain. Selected from hydrocarbyls of 1 to 24 carbon atoms which may be included in More preferably, R ¹¹ is selected from hydrogen and hydroxyl or hydrocarbyl of 1 to 24 carbon atoms which may be optionally substituted by alkoxy of 1 to 4 carbon atoms.

In a preferred embodiment, R ¹² is selected from hydrogen and alkyl of 1 to 4 carbon atoms. More preferably, R ¹² is selected from hydrogen and a methyl group.

In a preferred embodiment, R ¹³ is selected from hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms, or phenyl. More preferably, R ¹³ is hydrogen or methyl.

In a preferred embodiment, G is a direct bond, m and o are 0, and n is 4.

Further preferred embodiments include any combination of the above parameters.

Production Method The term "Lewis acid" refers to aluminum halide, alkyl aluminum halide, boron halide, tin halide, titanium halide, lead halide, zinc halide, iron halide, gallium halide, arsenic halide, copper halide, cadmium halide, It is intended to include mercury halides, antimony halides, and the like.
Preferred Lewis acids include aluminum trichloride, aluminum tribromide, methyl aluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium dichloride, tin tetrachloride, or mixtures thereof.

As used herein, the term “stepwise” means that a series of reactions is performed, with the first reaction producing a compound of formula (XXXII), (XXXV), or (XXXVI), Prior to the addition of the compound of (XXXIII), the reaction is carried out until progressing from about 50% to about 100%,
IV a / b / c) or (V). Preferably, the reaction is carried out prior to the addition of the compound of formula (XXXIII) until it has progressed between about 70% and about 100%, more preferably between about 75% and about 100%.

The novel benzo ring-substituted pyrimidines and triazines of the present invention have a benzo ring moiety (XX
X) and a halogen-substituted pyrimidine or triazine compound of the formula (XXXI) or (XXXIV). Schemes l, 2, and 3
I want to see.

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Wherein Hal is bromine, chlorine or iodine. Compound (XXX) is defined as a protonated compound of formula (X), as defined above. In compounds (XXXI) and (XXXIV), Hal is halogen, preferably bromine, chlorine, or iodine, and A, T, and Z are as defined above. In compound (XXXIII), L, X, T ′, Y, R ³ , and R ⁴ are as defined above.

The relative amounts of the reactants are as follows: The amount of compound (XXXI) or (XXXIV)
It must be in an amount sufficient to react with the benzo ring compound of formula (XXX) to form a compound of formula (XXXII), (XXXV), or (XXXVI). The amount of the benzo ring compound of formula (XXX) is sufficient to produce an undesired by-product such as tris benzo ring triazine or tris benzo ring pyrimidine without excessive amounts of formula (XXXII), (XXXV), or (XXXV
It is important to ensure the synthesis of the benzo ring compound of I). In addition, excess benzo ring compounds are enriched in mono- and tris-benzo ring triazines, or mono- and tris-benzo ring pyrimidines, making product separation and formation difficult and resource intensive. May lead to product distribution.

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The amount of the benzo ring compound (XXX) is 2-halo-4,6-bisbenzo ring-1,3,5-triazine
, 2,4-dihalo-6-benzo-ring-1,3,5-triazine, 2-halo-4,6-bisbenzopyrimidine, 2,4-dihalo-6-benzopyrimidine, or 2- Halo-4,6-bisbenzo ring-1,3.5-triazine is converted to 2,4,6-trisbenzo ring-1,3,5-triazine, or 2-halo-4,6-bisbenzo ring pyrimidine is converted to 2,2 Must be sufficient to convert to 4,6-trisbenzocyclic pyrimidine. Preferably, there should be between about 1 and about 5 molar equivalents of the benzo ring compound of formula (XXX) relative to the compound of formula (XXXI) or (XXXIV). The amount of the aromatic compound of the formula (XXXIII) is determined by the formula (XXXII), (XX
XV) or between about 0.5 and about 2.5 molar equivalents of the compound of formula (XXXIII
) Must be an aromatic compound.

The amount of the Lewis acid, Al (Hal) ₃ , wherein Hal is a halide as defined above, used in this reaction is 2,4,6-trishalo-1,3 , 5-triazine or 2
, 4,6-Trihalo-pyrimidines are each a preferred 2-halo-4,6-bisbenzo ring-
1,3,5-triazine, 2,4,6-trisbenzo ring-1,3,5-triazine, or 2-halo-4
It must be sufficient to convert to 2,6-bisbenzopyrimidine and 2,4,6-trisbenzopyrimidine. The amount of Lewis acid should be between about 0.5 to about 500 molar equivalents. Preferably, the amount of Lewis acid should be between about 1 to about 5 molar equivalents.

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The Lewis acid is a benzo ring compound of formula (XXX), a compound of formula (XXXI) or (XXXIV),
Or with either of the two in any manner. The preparation of the reaction mixture in the system is independent of the order of addition, at least one compound of formula (XXXI) or (XXXIV), at least one benzo ring compound of formula (XXX), and optionally at least one solvent. Adding two Lewis acids. As used herein, one or more Lewis acids are used, and the Lewis acids in the first and second steps are the same or different.

The reaction must be carried out at a temperature and pressure sufficient for synthesizing the desired triazine or pyrimidine compound for a sufficient time. Expression (XXXII), (XXXV), (XXXVI)
The preferred reaction time for the synthesis of the compound of Formula I, ie, the first step, is between about 5 minutes and about 48 hours, more preferably between about 15 minutes and about 24 hours. Equations (1), (I
The preferred reaction time for the synthesis of the compounds of (V a / b / c), (V), ie the second step, is between about 10 minutes and about 24 hours, more preferably the time is about 30 minutes And about
It is between 12 hours. The reaction pressure is not critical and can be about 1 atmosphere or even higher if desired. Preferably, the reaction is performed under an inert gas such as nitrogen or argon. Those of ordinary skill in the art with little or no experience will be able to determine the reaction temperatures required to obtain the desired product.

This stepwise process comprises the at least one Lewis acid and the formula (XXXI) or (
XXXIV) and one or more desired benzocyclic compounds of formula (XXX)
Preferably, it comprises mixing until the reaction has progressed between about 70% and about 100%. Thereafter, the product is isolated and purified. To synthesize a compound of formula (I), (IV a / b / c) or (V), an aromatic compound of formula (XXXIII) is added to the purified product together with a Lewis acid. The stepwise sequence allows the compound of formula (XXXII), (XXXV), or (XXXVI) to be isolated, purified, and stored prior to subsequent reaction with the aromatic compound of formula (XXXIII) .

In order to synthesize compounds of formulas (1), (IV a / b / c), (V), a compound of formula (XXXI
A preferred addition time of the aromatic compound of II) is between about 5 minutes and about 10 hours, a more preferred addition time is between about 10 minutes and about 5 hours, and a most preferred addition time is about 1 hour.
Between 5 minutes and about 2 hours.

The Lewis acid must be present in an amount sufficient to react with the number of substituted halogens of the compound of formula (XXXI) or (XXXIV). A range of between about 1 to about 5 molar equivalents of Lewis acid can be used. The preferred Lewis acid is aluminum chloride. Preferred amounts of Lewis acids are about halo-triazine or halo-pyrimidine.
2 to about 4 molar equivalents.

The synthesis of the compounds of formula (VI), (VII), VIII), or (IX) may be performed by methods commonly known in the art. Those of ordinary skill in the art with little or no experience will be able to determine the appropriate conditions to obtain the desired polymer product.

Use of Benzo Ring-Substituted Pyrimidines and Triazines As indicated above, the novel benzo ring-substituted pyrimidines and triazines of the present invention can be used, for example, in various polymers (both crosslinked and thermoplastic), photographic It is particularly useful as a UV light absorber for stabilizing a wide variety of materials, including dye solutions for materials and textile materials, and UV screens (sunscreens). The novel benzo ring-substituted pyrimidines and triazines of the present invention can be used, for example, as components in light-stabilizing compositions such as coatings or solutions, or as UV
As a component in the cutting composition, included in such a material in any of a variety of conventional ways, including physical mixing or blending, optionally with chemical bonding to the material (usually to a polymer). Can be done.

In one embodiment of the present invention, the benzo-ring-substituted pyrimidines and triazines of the present invention are prepared by chemically or physically incorporating the compound claimed in the present invention into a polymer material. It can be used to stabilize materials that are subject to degradation by. Non-limiting examples of polymer materials so stabilized are:
Polyolefin, polyester, polyether, polyketone, polyamide, natural and synthetic rubber, polyurethane, polystyrene, high impact polystyrene, polyacrylate, polymethacrylate, polyacetal, polyacrylonitrile, polybutadiene, polystyrene, ABS, SAN (styrene-acrylonitrile), ASA (
(Acrylate-styrene-acrylonitrile), cellulose acetate butyrate, cellulose polymer, polyimide, polyamideimide, polyetherimide,
Polyphenyl sulfide, PPO, polysulfone, polyether sulfone, polyvinyl chloride, polycarbonate, polyketone, aliphatic polyketone, thermoplastic TPO, amino resin crosslinked polyacrylate and polyester, polyisocyanate, crosslinked polyester and polyacrylate, phenol / formaldehyde,
With urea / formaldehyde and melamine / formaldehyde resins, dry and non-dry alkyd resins, alkyd resins, polyester resins, acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins, anhydrides or amines Crosslinked, crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds,
Polysiloxanes, Michael addition polymers, amines, blocked amines with activated unsaturated compounds and methylene compounds, ketimines with activated unsaturated compounds and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, unsaturated Polyketimines in combination with acrylic resins, radiation curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based paper formulations, photographic film papers, inks, and blends thereof.

[0125] Preferred polymeric materials are selected from the group consisting of: Polyolefin;
Copolymers of one or more monoolefins and / or diolefins with carbon monoxide and / or other vinyl monomers; hydrogenated modifications thereof and hydrocarbon resins containing mixtures of polyalkylenes and dendrites (C ₅ -C ₉ etc.); polyester;
Copolyetheresters; polyethers; polyketones; polyimides and copolyamides derived from diamines, dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams; natural and synthetic rubbers and elastomers; polyurethanes; polystyrene, poly-α-methylstyrene and Copolymers with other vinyl monomers; graft copolymers of styrene; high-impact polystyrene; polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile; unsaturated alcohols and amine or acyl derivatives or these Homo- and copolymers, such as polyvinyl alcohol polyvinyl acetate, polyacetal, and polybutyral, derived from the acetal of alkylene glycol and alkylene Homo- and copolymers of cyclic ethers such as oxide, and copolymers with bisglycidyl ether; polybutadiene; polystyrene; ABS (acrylonitrile-butadiene-styrene); SAN (styrene-acrylonitrile); ASA (acrylate-styrene-acrylonitrile); cellulose acetate Butyrate; Cellulose polymer; Polyurea; Polyimide; Polyamide-imide; Polyester-imide; Polyether-imide; Polyhydantoin;
Polybenzimidazole; Polyphenylsulfide; PPO (polypropylene oxide); Polysulfone; Polyethersulfone; Polyetherketone; Halogen-containing polymer; Polyvinylchloride; Polycarbonate; Polyestercarbonate; Thermoplastic TPO; Amino-resin crosslinked polyacrylate and polyester; Ne cross-linked polyester and polyacrylate; phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins;
Saturated and unsaturated polyester resins; crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylate, hydroxy acrylate, isocyanatoacrylate, urethane acrylate or polyester acrylate; alkyd resins, polyester resins, and melamine resins crosslinked acrylate resins, urea resins , Isocyanate, isocyanurate, carbamate, or epoxy resin
Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and / or aromatic anhydrides or amine-bridged glycidyl compounds; polysiloxanes; activated unsaturated compounds of amines and blocked amines and methylene compounds Michael addition polymers with e.g. ketimines; activated unsaturated compounds such as acrylates and methacrylates, maleates and acetoacetates and ketimines with methylene compounds; unsaturated acrylics in combination with polyacetoacetate resins or unsaturated acrylic resins Polyketimines; radiation-curable compositions; epoxy melamine resins; natural polymers such as cellulose, rubber, gelatin, and chemically modified derivatives thereof; organic dyes and pigments; mixtures or blends of the above; cosmetics; Film paper An ink; and an intraocular lens.

Further non-limiting examples of particular polymers to be stabilized include: l. Ethylene, propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, cyclopentene and norborneneethylidene and cycloolefins; for example, high density polyethylene (HDPE) High density and high molecular weight polyethylene (HDPE-HMW), High density and high molecular weight polyethylene (HDPE-UHMW), Medium density polyethylene (MDPE), Low density polyethylene (LDPE), Linear low density polyethylene (LLDPE)
Mono- and di-olefin homo- and copolymers, including polyethylene (optionally cross-linkable), such as, for example, branched low-density polyethylene (BLDPE); and one or more mono- and / or di-olefins. Carbon monoxide and / or acrylic and methacrylic acid, acrylate and methacrylate, acrylamide, acrylonitrile, styrene, vinyl acetate (ethylene / vinyl acetate copolymer, etc.), vinyl halide, vinylidene halide, maleic anhydride and allyl alcohol, allylamine, allyl Copolymers with other vinyl monomers, including allyl monomers such as glycidyl ether and derivatives thereof 3. Hydrocarbon resins (C ₅ -C ₉ etc.) containing these hydrogenated products and mixtures of polyalkylenes and starch ), 4. Homo-styrenes such as styrene, p-methylstyrene and α-methylstyrene
And other vinyl monomers such as styrene and one or more olefins and diolefins (eg, ethylene, isoprene, and / or butadiene), acrylic and methacrylic acids, acrylates and methacrylates, acrylamides, acrylonitriles. , Vinyl acetate (ethylene / vinyl acetate copolymer, etc.), vinyl halide, vinylidene halide, maleic anhydride and copolymers with allyl compounds such as allyl alcohol, allylamine, allyl glycidyl ether and derivatives thereof, 6. polybutadiene, polybutadiene / styrene copolymer And polybutadiene /
Graft copolymer of styrene on acrylonitrile copolymer; graft copolymer of styrene (α-methylstyrene) and acrylonitrile (or methacrylonitrile) on polybutadiene; graft copolymer of styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and anhydride on polybutadiene Graft copolymer of maleic acid or maleimide, graft copolymer of styrene and acrylonitrile on ethylene / propylene / diene copolymer, graft copolymer of styrene and acrylonitrile on polyalkyl acrylate or methacrylate, and graft of styrene and acrylonitrile on acrylate / butadiene copolymer Copolymer, 7. polychloroprene; chlorinated rubber; chlorination and odor Chlorinated or chlorosulfonated polyethylene; copolymers of ethylene and chlorinated ethylene; epichlorohydrin polymers and copolymers, halogen-containing vinyls such as vinyl chloride, vinylidene chloride, vinylidene fluoride and / or vinylidene fluoride 8. Halogen-containing polymers such as polymers and copolymers of compounds and other vinyl monomers, 8. Derived from α, β-unsaturated acids such as acrylic acid, methacrylic acid, acrylate, methacrylate, acrylimide and acrylonitrile and derivatives thereof. 9. Monomers and olefins and diolefins (eg butadiene), styrene, vinyl halides, maleic anhydride and allyl alcohol Copolymers with other unsaturated monomers such as allyl monomers such as allylamine, allylamine, allylglycidyl ether and derivatives thereof; 10. vinyl alcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol Homo- and copolymers derived from unsaturated alcohols and amines, such as allylamine, allyl glycidyl ether, allyl phthalate and allyl melamine, or their acyl derivatives or acetals, as well as such monomers and other ethylene types mentioned above. Copolymers with unsaturated monomers, (for polymers of the above group of 1-lO, the present invention further includes those polymers as produced by metallocene catalysis) 11. Alkylene glycols and amines Homo of cyclic ethers, such as sharp emission oxide
-And copolymers, and copolymers with bisglycidyl ethers, 12. polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; and polyacetals such as polyoxymethylene modified with thermoplastic polyurethanes, acrylates and / or MBS; 14. Polyphenylene oxides and sulfides, 14. Polyurethanes derived from hydroxy-functional components such as polyhydric alcohols, polyethers, polyesters, polyacryls and / or polybutadienes on the one hand and aliphatic and / or aromatic isocyanates on the other hand. And their precursors, 15. Polyamide 4, Polyamide 6, Polyamide 6/6, Polyamide 6/1 O, Polyamide 6/9, Polyamide 6/12, Polyamide 4/6, Polyamide 12/12, Polyamide 11
Polyamides and copolyamides derived from diamines, dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams such as polyamide 12; aromatic polyamides starting from m-xylylenediamine and adipic acid; Polyamides made from hexamethylenediamine and isophthalic acid and / or terephthalic acid without addition, such as poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide;
A block copolymer of the above polyamide with a polyolefin, olefin copolymer, ionomer, chemical bond or graft elastomer, or a polyether such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and a polyamide condensed during processing (RIM polyamide series), 1 6. Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole, l 7. Polyethylene terephthalate, polybutylene terephthalate, poly-1,4-
Polyesters derived from dicarboxylic acids, such as dimethylcyclohexane terephthalate and polyhydroxybenzoate, diols and / or hydroxycarboxylic acids or the corresponding lactones, and block copolyetheresters derived from hydroxy-terminated ethers, PETG, PEN, PTT, and also Polyester modified with polycarbonate or MBS, 18. Polycarbonate and polyester carbonate, 19. Polysulfone, polyether sulfone and polyether ketone, 20. Aldehyde condensation resins such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin Crosslinked polymers derived, 21. dry and non-dry alkyd resins, 22. saturated and unsaturated dicarboxylic acids and polyhydric alcohols 23. Unsaturated polyester resins derived from copolyesters and vinyl compounds as crosslinking agents and also from these halogen-containing modifiers, 23. From substituted acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester acrylates Induced cross-linked acrylic resin, 24. Melamine resin, urea resin, alkyd resin, polyester resin cross-linked by isocyanate, isocyanurate, carbamate or epoxy resin
25. a crosslinked epoxy resin derived from an aliphatic, cycloaliphatic, heterocyclic and / or aromatic glycidyl compound such as bisphenol A and bisphenol F, crosslinked by a curing agent such as anhydride or amine; 26. Naturally-modified polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, including cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose, and rosin and their derivatives; 28. Michael addition polymers of amines or blocked amines (eg ketimines) with activated unsaturated and / or methylene compounds such as acrylates and methacrylates, maleate and acetoacetate, 29. PP / EPDM, Polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS,
PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic polyurethane, POM / acrylate, POM / MBS, PPO / H
IPS, PPO / PA6.6 and copolymer, PATENT / HDPE, PP / HDPE, PP / LDPE, LDPE / H
DPE. LDPE / EVA, LDPE / EAA, PATENT / PP, PATENT / PPO, PBT / PC / ABS, PBT / PET
A mixture or blend of any of the above, such as / PC, 30. unsaturated acrylic polyacetoacetate resin or urethane acrylate,
31. Polyether acrylates, vinyl or acrylic copolymers with pendant unsaturated groups, and polyketimines in combination with unsaturated acrylic resins, including acrylated melamines. 31. Radiation curable, including ethylenically unsaturated monomers or oligomers or polyunsaturated aliphatic oligomers 32. Light stable epoxy resins cross-linked with epoxy-functional co-etherified high solids melamine resins (other materials that can be stabilized include, for example) 33. Mineral oils, animal and vegetable fats and oils, and Wax, or synthetic ester (e.g.,
Natural or synthetic organic materials, which are mixtures of compounds, including fats and oils based on phthalates, adipates, phosphates or trimellitates) and mixtures of mineral oils of any ratio of waxes and also synthetic esters, 34. Natural latex or carboxylation Aqueous emulsion of natural or synthetic rubber such as styrene / butadiene copolymer latex, 35. azo dye (diazo, triazo and polyazo), anthraquinone, benzodifuranone, polycyclic aromatic carbonyl dye, indigo dye, polymethine, styryl dye, di- and Tri-arylcarbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes,
Organic dyes such as quinacridone, carbazole and perylenetetracarboxylic diimide; 36. synthetic materials such as antioxidants, preservatives, lipids, solvents, surfactants, coloring agents, antiperspirants, skin conditioners, humectants and collagen; Contains natural products such as protein, mink oil, olive oil, coconut oil, camauba wax, bee wax, lanolin, cocoa butter, xanthan gum, aloe, skin lotion, collagen cream, UV cut agent, facial makeup, etc. Cosmetic products, 37. Newsprint, cardboard, posters, packaging, labels, stationery, book and magazine paper, bond-type paper, multipurpose and office paper, computer paper, Xerox paper, laser and inkjet printer paper, office paper 38. Cellulose-based paper formulations for paper, banknotes, etc., 38. Photographic film paper, 39. Inks.

Aliphatic Polyamides The novel benzo-substituted pyrimidines and triazines of the present invention can also be used with aliphatic polyamide polymers. "Aliphatic polyamides" are polyamides characterized by the presence of carbon amide groups that repeat as part of a polymer chain separated from each other by at least two aliphatic carbon atoms.
These polyamides are exemplified by the general formula -NHC (O) RC (O) NHR ¹ -or -NH-RC (O)-(wherein R and R ¹ are the same or different and at least about 2 Or an alkylene group, preferably an alkylene group having about 2 to about 12 carbon atoms) or a combination thereof. Examples of such polyamides include poly (tetramethylene adipamide) (nylon 4,6); poly (hexamethylene adipamide) (nylon 6,6); poly (hexamethylene azelamide) (nylon 6 , 9); poly (hexamethylene sebacamide) (nylon 6,1O); poly (heptamethylenepimelamide) (nylon 8,8); poly (nonamethylene azelamide) (nylon 9,9); poly (Decamethyleneazelaamide) A polyamide formed by the reaction of a diamine such as (nylon 10, 9) with a dibasic acid. Examples of useful aliphatic polyamides include those formed by polymerization of amino acids and their derivatives, for example, lactams. Examples of these useful aliphatic polyamides include poly (4-aminobutyric acid) (nylon 4); poly (6-aminohexanoic acid) (nylon 6); poly (7-aminoheptanonic acid) (nylon 7); Poly (8-aminooctanoic acid) (nylon 8); poly (9-aminononanoic acid) (nylon 9); poly (10-
Aminodecanoic acid) (nylon 10); poly (11-aminoundecanoic acid) (nylon 11);
Poly (12-aminododecanoic acid) (nylon 12). Also, blends of two or more aliphatic polyamides are used.

Copolymers formed from combinations of the above-recited aliphatic polyamide repeating units can be used. By way of example, and not limitation, such aliphatic polyamide copolymers include caprolactam / hexamethylene adipamide (nylon 6 / 6,6); hexamethylene adipamide / caprolactam copolymer (nylon 6, 6/6 Hexamethylene adipamide / hexamethyleneazelaamide copolymer (nylon 6,6 / 6,9); and formed from aliphatic polyamide repeating units and aliphatic / aromatic polyamide repeating units cited above. Copolymers are also used. Examples of such copolyamides are nylon 6 / 6T, nylon 6,6 / 6, T, nylon 6 / lOT, nylon 6 / 12T, nylon 6,10 / 6, T and the like.

Preferred aliphatic polyamides for use in the practice of the present invention are poly (caprolactam), poly (7-aminoheptanonic acid), poly (tetramethylene adipamide), poly (hexamethylene adipamide) And mixtures thereof. Particularly preferred aliphatic polyamides are poly (caprolactam), poly (hexamethylene adipamide)
, Poly (tetramethylene adipamide) and mixtures thereof.

[0130] Aliphatic polyamides useful in the practice of the present invention can be obtained from commercial sources or produced by known synthetic techniques. For example, polycaprolactam is obtained from Allied Signal Inc, and poly (hexamethylene adipamide) is obtained from DuPont Co.

The number average molecular weight of the aliphatic polyamide varies widely. Generally, aliphatic polyamides are of a film-forming molecular weight high enough to produce a self-supporting film and low enough to allow melt processing of the blend into a film. Such number average molecular weights are known to film experts and are usually at least about 5,000 as determined by the formic acid viscosity method. In this method, 9.2% by weight in 90% formic acid
A concentrated aliphatic polyamide solution is used at 25 ° C. In a preferred embodiment of the present invention, the aliphatic polyamide has a number average molecular weight of about 5,000 to about 1,000,000,
In a particularly preferred embodiment, from about 10,000 to about 100,000. Of the particularly preferred embodiments, most preferred are those wherein the average molecular weight of the aliphatic polyamide is about 20.
From about 000 to about 40,000.

Polyurethane Polyurethane (PUR) elastomer products ("Spandex") can be stabilized against discoloration and loss of elasticity upon exposure to UV light by a combination of a UV absorber and a hindered amine light stabilizer according to the present invention. Spandex fiber is a PUR elastomer product that requires very specific UV absorber and hindered amine light stabilizer properties to achieve optimal performance. The triazine UV absorbers of the present invention, combined with polymeric hindered amine light stabilizers (HALS), provide outstanding performance in obtaining the desired properties for spandex fiber applications.

The triazine UV absorbers of the present invention, used alone or in combination with HALS, provide the following properties in spandex fiber applications: (1) low color contribution at normal use levels in the range of 0.5-2.0%; (2) sufficient MW and thermal stability for fiber processing and heat exposure conditions, fiber processing and heat exposure conditions (3) high compatibility and persistence; (4) prevention of discoloration and loss of elasticity upon exposure to UV light energy; (5) low extraction with water and dry cleaning solvents. (6) low color development upon exposure to air pollutants, NO _x , SO _x , hydrocarbons, etc .; (7) low interaction with seawater and pool chemicals; (8) spandex fiber. Low interaction with the usual phenolic antioxidants used for thermal stabilization and low color development; and (9) interaction with the copper-based antioxidants used in nylon fibers for nylon / spandex fibers. The effect is low.

[0134] were added to polymeric HALS, or no addition of triazine UV absorbers, coloration progresses at the time of NO _x exposure is low, and interaction with copper based antioxidant systems used in Nylon fibers is low Negative effects on secondary performance, such as, provide minimal and excellent stabilization.

As noted above, any of the triazine compounds disclosed herein are used to impart one or more of the above properties to the spandex fiber when added in a stabilizing effective amount. .

Preferably, these triazine compounds are added in combination with polymer type HALS. Polymeric HALS is preferably poly [(6-morpholino-s-triazine-2,
4-diyl) [2,2,6,6, -tetramethyl-4-piperidyl) imino] -hexamethylene [(2
, 2,6> 6-Tetramethyl-4-piperidyl) imino]. Most preferably, polymeric HALS is the methylated (M) products of the HALS, which Cytec Industries (Cytec Industries, Inc.) sold as CYASORB ^R UV-3529 light stabilizer by. Other polymeric HALS described in U.S. Pat. No. 4,331,586 are also suitable.

[0137] Spandex fibers are made from polyurethane (PUR) prepolymers made from diisocyanates and glycols. There are four basic processes used to convert PUR prepolymers into textiles. These processes are solution dry spinning, solution wet spinning, melt extrusion, and reactive spinning. The above UV stabilizers alone or in combination with HALS are suitable for use in any or all of the four processes.

The spandex fibers include a processing antioxidant system, such as a phenolic antioxidant or a phenolic / phosphite antioxidant combination. In addition, pigments such as Ti0 ₂ are commonly used in textile products.

The triazine UV absorber alone or in combination with HALS can be dissolved in DMF or DMAC and added to the PUR prepolymer solution prior to the solution fiber spinning process. The combination can also be extruded into the PUR compound used in the melt spinning process.

[0140] benzo ring of polycarbonate novel invention - of the polymeric material of the subject being stabilized by substituted pyrimidines and triazines, polycarbonates, polyesters, polyamides,
Polyacetal, polyphenylene oxide and polyphenylene sulfide are preferred, and polycarbonate is particularly preferred. These compounds have, in particular, a repeating structural unit of the formula

[0141]

Embedded image

Embedded image where A is a divalent phenol group.

Examples of A are given, inter alia, in US Pat. No. 4,960,863 and DE-A-3 922,496.
For example, hydroquinone, resorcinol, dihydroxybiphenylene or bis (hydroxyphenyl) alkane, cycloalkane, sulfide, ether,
Ketones, sulfones, sulfoxides, α, α′-bis (hydroxyphenyl) -diisopropylbenzene, for example, the compound 2,2-bis (4-hydroxyphenyl) propane,
2.2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. , From bisphenols in the broadest sense of the term, or from the formula

[0144]

Embedded image

[0145]

Embedded image

A is derived from the compound of

In one embodiment, preferred resins are 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 2.4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1- Bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-
Polycarbonate based on dihydric phenols such as chloro-4-hydroxyphenyl) propane, 4,4'-sulfonyldiphenol, and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane It is.

Also preferred are polycarbonate copolymers containing two or more phenols, branched polycarbonates in which a polyfunctional aromatic compound has been reacted with a dihydric phenol and a carbonate precursor, and polycarbonates having a substantial portion of the blend. A polymer blend comprising:

The most preferred resins for both layers are polycarbonates based on bisphenol A. U.S. Pat.No. 5,288,788 also discloses polycarbonates and polyester carbonates, especially aromatic polycarbonates such as 2,2-bis (4
Those based on -hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane have also been described.

Multi-layer UK Patent Application No. 2,290,745 describes a polymer material near or near the surface.
A number of methods have been described that have been developed to concentrate UV absorbers. They are,
Surface impregnation (U.S. Pat.Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937
, 026) and a solution comprising a thermoplastic resin and a UV absorber (see US Patent Nos. 4,668,588 and 4,353.965). Both methods have the disadvantage of requiring additional process steps (ie, coating, drying or curing) and encounter difficulties associated with handling large processed articles. A further disadvantage, especially related to the production of polycarbonate sheets, is the detrimental effect of such post-addition treatments on the surface of the polymer substrate.

As described in US Pat. No. 5,445,872, application of a surface layer by co-extrusion is accomplished by known co-extrusion equipment as taught in US Pat. Nos. 3,487,505 and 3,557,265. Done in a way. Co-extrusion is a well-recognized method of manufacturing a laminated thermoplastic material by simultaneously extruding a number of different layers to form a single composite material. U.S. Pat. No. 4,540,623 describes at least 40 layers of co-extruded material. Other methods produce as few as two or three different layers.

In one embodiment, the present invention also relates to a method comprising 0.1 to 10 mils (0.00254 mm to
0.254 mm), preferably 0.1 to 5 mil (0.00254 mm to 0.127 mm) thick thermoplastic layer, said layer containing 0.1% to 20% by weight of the inventive benzo-ring-substituted pyrimidines and triazines. To a thermoplastic article. Preferred concentration is from 20
15% by weight, the most preferred concentration being 5% to 10% by weight.

The benzo-ring-substituted pyrimidines and triazines of the present invention are incorporated into the surface layer thermoplastic resin by standard methods such as dry mixing the additives with the granular resin prior to extrusion. The benzo ring-substituted pyrimidine or triazine layer is applied to one or both sides of the thermoplastic article.

A laminated thermoplastic article that includes additional layers, such as a water resistant layer as found in US Pat. No. 4,992,322, is also part of the invention.

The core layer and the coating layer may be made of copolymers and blends of styrene and acrylonitrile and styrene and maleic anhydride on polyester, polyester carbonate, polyphenylene oxide, polyvinyl chloride, polypropylene, polyethylene, polyacrylate, polymethacrylate and polybutadiene. And the same or different thermoplastics, including mixtures (polyblends) of such polymers with other polymers such as polyolefins, polyacrylates, polydienes or other elastomers in the form of impact modifiers.

Bound Stabilizers The benzo-ring-substituted pyrimidines and triazines of the present invention can also be chemically bonded to a substrate, such as a polymer, such that, for example, UV radiation from the substrate or from the substrate surface It greatly reduces the migration of the absorbent. The coupling mechanism of the triazines of the present invention involves the formation of a bond (chemical and / or covalent bond) between a functional group attached to an amide or carbamate group with a pendant vinyl or hydroxyl group and a "host" substrate such as a polymer.

The inclusion of the benzo-ring-substituted pyrimidines and triazines of the present invention is described in a manner as disclosed in US Pat. Nos. 3,423,360 and 5,189,084, which are incorporated herein by reference. It can be carried out by polymerization, copolyaddition, copolycondensation, by reaction with a polymer having suitable functional groups, or by grafting.

The coupling of the benzo ring-substituted pyrimidines and triazines of the present invention can occur by polymerization or copolymerization. In the case of the novel triazines of the invention comprising pendant vinyl groups, at least one vinyl monomer, for example (meth) acrylates such as (meth) acrylic acid, methyl acrylate, (meth) acrylamide, hydroxy Polymerization or copolymerization with ethyl acrylate, olefin, vinyl chloride, styrene, butadiene, isoprene, and acrylonitrile can be performed to form a homopolymer or copolymer in which vinyl groups are included in the polymer backbone. As is known to those skilled in the polymerization arts, initiators such as free radical, anionic and cationic types, or UV, electron, x-ray and Co
Polymerization or copolymerization can be initiated by actinic radiation, such as gamma radiation from a source. As is known to those skilled in the polymerization arts, polymerization or copolymerization can be performed in solution, emulsion, dispersion, or in a molten, solid phase.

The bond of the claimed benzo-ring-substituted pyrimidine and triazine compounds of the present invention can also be formed by copolyaddition or copolycondensation. Such inclusion can be achieved by additions during the synthesis of the addition polymer or copolymer or condensation during the synthesis of the condensation polymer or copolymer by methods known to those skilled in the art.

For example, a compound of formula (1), (II), or (IV)-(IX) containing a suitable functional group
To name a few, it may be included in polyesters, polyamides, polyurethanes, epoxy resins, melamine resins, alkyd resins, phenolic resins, polyurethanes, polycarbonates, polysiloxanes, polyacetals and polyanhydrides.

In addition, a compound of formula (1), (II), or (IV)-(IX) may be attached to a monomer component to form a polymer or copolymer, for example, by the free radical initiated addition or copolycondensation method described above. Can be contained within. A similar method of attaching benzotriazole and benzophenone stabilizers to a diol precursor and incorporating it into polyurethanes and polyesters by condensation polymerization to impart UV stability to the polymer is described, for example, in U.S. Pat. Is included by reference for all purposes).

Alternatively, the benzo-substituted pyrimidines and triazines of the present invention can also be attached to polymers by reaction with oligomers and / or polymers having suitable functional groups. For example, a triazine compound comprising at least one pendant vinyl group, optionally together with at least one other vinyl monomer or a compound comprising a vinyl group, is converted into an unsaturated polyester resin, an unsaturated polybutadiene oligomer or an unsaturated rubber. It can be added and then cured by actinic radiation or by a free radical catalyst. Alternatively, at least one triazine compound having a terminal functional group such as hydroxyl or amide in the main chain or side chain can be obtained by a method similar to those known to those skilled in the art, such as polyester, polyurethane having a reactive terminal group, and polydiol. , Partially hydrolyzed with a polymer and / or oligomer, such as a polymer comprising polyvinyl acetate, epoxy resin, polysiloxane and maleic anhydride.

Grafting is another method of attaching the benzo-ring-substituted pyrimidines and triazines claimed in the present invention to polymers and / or oligomers. For example, when using the novel triazines of the present invention comprising pendant vinyl groups, the grafting is carried out in solution, melt, or in the solid phase with the initiators or actinic radiation described above for the polymerization. Such benzo ring-substituted pyrimidines and triazines can be found in saturated polymers such as polyethylene, polypropylene and polyolefins such as poly (ethylene-vinyl acetate) and their copolymers, or polymers containing unsaturated sites, such as polybutadiene, polyisoprene, ethylene
Grafted onto -propylene- (diene monomer) terpolymers and polystyrene and its copolymers.

The benzo-ring-substituted pyrimidines and triazines of the present invention are used in widely varying amounts in applications that depend on the material to be stabilized and the like and in specific applications. However, when used as a stabilizing additive for materials such as organic polymers,
The benzo-ring-substituted pyrimidines and triazines of the present invention typically contain from about 0.01 to about 20% by weight, preferably from about 0.1 to about 100% by weight, and most preferably from about 0.1 to about 10% by weight, based on the weight of the material to be stabilized. Used in an amount of about 5% by weight. In the use of ultraviolet ray cutting such as an ultraviolet ray cutting composition, the triazine is used in the same relative amount but based on the total weight of the ultraviolet ray cutting agent.

The novel stabilizers of the present invention are also used in non-binding capacity, for example in the stabilization of thermoplastic polymers as set forth in the references included above. Examples of preferred thermoplastic polymers are polyolefins and polymers comprising heteroatoms in the main chain. Preferred polymers are also thermoplastic polymers comprising nitrogen, oxygen and / or sulfur in the main chain, especially nitrogen or oxygen. Also of interest are compositions where the polymer is a polyolefin, such as polyethylene or polypropylene.

The incorporation into the thermoplastic polymer can be carried out by the methods customary in the art by the addition of novel benzo-substituted triazine or pyrimidine compounds and further optional additives. Inclusion can be before or during molding, for example, by mixing the powder components, by adding a stabilizer to the polymer melt or solution, or by applying a compound dissolved or dispersed in the polymer, and subsequently evaporating or evaporating the solvent. It can be conveniently performed by a method that does not evaporate. Elastomers can also be stabilized as latex. Also, for example, the novel mixture can be added to the polymer to be stabilized in the form of a masterbatch containing these compounds at a concentration of about 2.5 to about 25%, preferably about 5 to about 20% by weight of the polymer. . The novel mixture may be conveniently included in the polymeric material by any number of methods, including those commonly used in the art, such as: For example: a) as an emulsion or dispersion (e.g., latex or emulsion polymer); (b) as a dry mix when mixing additional components or polymer mixtures; (c) processing equipment (e.g., extruders, internal mixers, etc.) Or (d) as a solution or melt.

The stabilized polymer composition thus obtained may be prepared by any number of conventional methods
For example, by hot pressing, spinning, extruding, funneling or injection molding, it can be converted into molded articles, such as fibers, films, tapes, sheets, sandwich boards, containers, pipes and other shapes.

The present invention therefore additionally relates to the use of the polymer compositions according to the invention for the production of molded articles.

Depending on the final end use, the benzo ring-substituted pyrimidines and triazines of the present invention are combined with various additives customary in UV stabilization technology. Such additives include, but are not limited to:

A. Antioxidants (i) 2,6-t-butyl-4-methylphenol; 2-t-butyl-4,6-dimethylphenol;
2,6-di-t-butyl-4-ethylphenol; 2,6-di-t-butyl-4-n-butylphenol; 2,6-di-t-butyl-4-isobutylphenol; 2,6- Dicyclopentyl-4-methylphenol; 2- (α-methylcyclohexyl) 4,6-dimethylphenol; 2,6-
Dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; 2
2,6-di-t-butyl-4-methoxymethylphenol; nonylphenol having a linear or branched side chain such as 2,6-di-nonyl-4-methylphenol; 2,4dimethyl-6- (1 -
Methylundec-1-yl) phenol; 2,4-dimethyl-6- (1-methylheptadec-1-
Yl) phenol; 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol; and alkylated monophenols such as a mixture thereof (ii) 2,4-dioctylthiomethyl-6-t-butylphenol; Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-ethylphenol; and 2,6-di-dodecylthiomethyl-4-nonylphenol, (iii) 2 2,6-di-t-butyl-4-methoxyphenol; 2,5-di-t-butylhydroquinone; 2,5-di-t-amylhydroquinone; 2,6-diphenyl-4-octadecyloxyphenol; 2, 6-di-t-butylhydroquinone; 2,5-di-t-butyl-4-hydroxyanisole; 3,5-di-t-butyl-4-hydroxyanisole; 3,5-di-t-butyl-
4-hydroxyphenyl stearate; and hydroquinones and alkylated hydroquinones such as bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate, (iv) α-tocopherol, β-tocopherol, γ-tocopherol, δ Tocopherols, such as -tocopherol and mixtures thereof (vitamin E); (v) 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol); 4 , 4'-thiobis (6-t-butyl-3-methylphenol); 4,4'-thiobis (6-t-butyl-2-methylphenol); 4.4'-thiobis (3,6-di-s- (Amylphenol); and a hydroxyated thiodiphenyl ether such as 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide; (vi) 2,2'-methylenebis (6-t-butyl-4- 2,2′-methylenebis (6-t-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 (4,6-di-t-butylphenol); 2,2'-ethylidenebis (4,6-di-t-butylphenol); 2,2'-ethylidenebis (6-t-butyl-4-isobutylphenol );
2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol]; 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol]; 4,4'-methylenebis (2,6-di-t-butylphenol); 4,4′-methylenebis (6-t-butyl-2-methylphenol); 1,1-bis (5-t-butyl) -4-hydroxy-2- Methyl-phenyl) butane; 2.6-
Bis (3-t-butyl-5-methyl-2-hydroxy-1-benzyl) -4-methylphenol; 1,1
, 3-Tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane; 1,1-bis (5-t-
Butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane; ethylene glycol bis [3,3-bis (3'-t-butyl-4'-hydroxyphenyl) butyrate], bis (3- t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene; bis [2- (3′-t-butyl-1-2′-hydroxy-5′-methylbenzyl) -6-t-butyl-4 -Methylphenyl] terephthalate; 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane; 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane;
2,2-bis (5-t-butyl) -4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane; and 1,1,5,5-tetra (5-t-butyl-1- 4-hydroxy-2-methylphenyl)
Alkylidene bisphenols such as pentane, (vii) 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether; octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate; Tridecyl-4-hydroxy-3,5-di-t-butylbenzylmercaptoacetate; tris
(3,5-di-t-butyl-4-hydroxybenzyl) amine; bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate; bis (3,5-di-t- Butyl-4
-Hydroxybenzyl) sulfide; and isooctyl-3,5-di-t-butyl-4-
O-N- and S-benzyl compounds such as hydroxybenzylmercaptoacetate, (viii) dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate; dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate; didodecylmercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate; and bis (4 -(1,1,3,3-tetramethylbutyl) phenyl]-
Hydroxybenzylate malonate such as 2,2-bis (3.5-di-t-butyl-4-hydroxybenzyl) malonate, (ix) 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -2,4,6-trimethylbenzene; 1,4-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene; and Aromatic hydroxybenzyl compounds such as 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) phenol; (x) 2,4-bis (butylmercapto-6- (3,5 -Di-t-butyl-4-hydroxyanilino)
-1,3,5-triazine; 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine; 2-octylmercapto- 4.6-screw (3,5
-Di-t-butyl-4-hydroxyphenoxy)-1,3,5-triazine; 2,4,6-tris (3,5
-Di-t-butyl-4-hydroxyphenoxy) -1,3,5-triazine; 1,3,5-tris (3,5-
Di-t-butyl-4-hydroxybenzyl) isocyanurate; 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate; 2,4,6-tris ( 3,5-
Di-t-butyl-4-hydroxyphenylethyl) -1,3,5-triazine; 1,3,5-tris (3,
5-di-t-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine; and triazines such as 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate Compound, (xi) dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphonate; diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5
-Di-t-butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-t-butyl
4-hydroxy-3-methylbenzylphosphonate; and benzylphosphonates such as calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester; (xii) 4-hydroxylauraanilide; Hydroxystearanilide; and acylaminophenol such as octyl N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate; (xiii) methanol, ethanol, n-octanol, i-octanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane and Mono- or polyhydric alcohols such as 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5-di
-t-butyl] -4-hydroxyphenyl) propionic acid ester, (xiv) methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene Glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundeca Monohydric or polyhydric alcohols such as phenol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid Stele, (xv) methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiol Diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl)
Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols,
(xvi) methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol , Diethylene glycol, triethylene glycol, pentaerythritol,
Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha -
Monohydric or polyhydric alcohols such as 2,6,7-trioxabicyclo [2.2.2] octane
Esters of 5-di-t-butyl-4-hydroxyphenylacetic acid, (xvii) N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine; N, N ' -Bis (3,5-di-t-butyl-1-4-hydroxyphenylpropionyl) trimethylenediamine; and N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine Amide of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and the like, (xviii) ascorbic acid (vitamin C), (xix) N, N′-diisopropyl-p-phenylenediamine; N, N'-di-s-butyl-p-phenylenediamine; N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine; N, N '
-Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine; N, N'-bis (1-methylheptyl) -p-phenylenediamine; N, N'-dicyclohexyl-p-phenylenediamine; N, N'-diphenyl-p-phenylenediamine; N, N'-bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N'-phenyl-p-phenylenediamine; N- (1,3
-Dimethylbutyl) -N'-phenyl-p-phenylenediamine; N- (1-methylheptyl
) -N'-phenyl-p-phenylenediamine;N-cyclohexyl-N'-phenyl-p-phenylenediamine; 4- (p-toluenesulfonamoyl) diphenylamine; N, N'-dimethyl-N.N'- Di-s-butyl-p-phenylenediamine; diphenylamine; allyldiphenylamine; 4-isopropyloxydiphenylamine; -phenyl-1-naphthylamine; N- (4-t-octylphenyl) -1-naphthylamine; N-phenyl-2- Naphthylamine; octylated diphenylamine such as p, p'-di-t-octyldiphenylamine;4-n-butylaminophenol;4-butyrylaminophenol;4-nonanoylaminophenol;4-decanoylaminophenol; 4- Octadecanoylaminophenol; bis (4-methoxyphenyl) amine; 2,6-di-t-butyl-4-dimethylaminomethylphenol; 2,4'-diaminophenylmethane;4,4'-diaminodiph N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane; 1,2-bis [(2-methylphenyl) amino] ethane; 1,2-bis (phenylamino) propane; (o-
Tolyl) biguanide; bis [4- (1 ′, 3′-dimethylbutyl) phenyl] amine; t-octylated N-phenyl-1-naphthylamine; a mixture of mono- and dialkylated t-butyl / t-octyldiphenylamine; Mixtures of mono- and dialkylated nonyldiphenylamines; mixtures of mono- and dialkylated dodecyldiphenylamines; mono-
And mixtures of dialkylated isopropyl / isohexyldiphenylamine, mono-
Mixtures of and dialkylated t-butyldiphenylamines; 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazole; phenothiazines; mono- and dialkylated t-
Mixture of butyl / t-octylphenothiazine; mixture of mono- and dialkylated t-octylphenothiazine; N-allylphenothiazine; N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene; N , N-bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylenediamine; bis (2,2,6,6-tetramethylpiperidid-4-yl)
Amine antioxidants such as sebacate; 2,2,6,6-tetramethylpiperidin-4-one; and 2,2,6.6-tetramethylpiperidin-4-ol.

B. UV-absorbers and light stabilizers (i) 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole; 2- (3 ′, 5′-di-
t-butyl-2'-hydroxyphenyl) benzotriazole; 2- (5'-t-butyl-2'-
(Hydroxyphenyl) benzotriazole; 2- (2'-hydroxy-5 '-(1,1,3,3-
(Tetramethylbutyl) phenyl) benzotriazole; 2- (3 ', 5'-di-t-butyl-2'-
(Hydroxyphenyl) -5-chlorobenzotriazole; 2- (3′-t-butyl-2′-hydroxy-5′-methylphenyl) -5-chlorobenzotriazole; 2- (3′-s-butyl-5
'-t-butyl-2'-hydroxyphenyl) -benzotriazole; 2- (2'-hydroxy-4
'-Octoxyphenyl) benzotriazole; 2- (3', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole; 2- (3 ', 5'-bis (α, α-dimethylbenzyl) ) -2
'-Hydroxyphenyl) -benzotriazole; 2- (3'-t-butyl-2'-hydroxy-5
A mixture of '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-5'-[2- (2-ethylhexyloxy) -carbonylethyl] -2 '-Hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-t-
Butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-
Benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5' -(2
-Octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl) benzotriazole, 2- (3 '-Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-t-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole; 2 , 2-methylenebis [4- (1,
1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'-t
Transesterification product of -butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; and [R-CH ₂ CH
-COO (CH ₂ ) ₃ ] ₂ B (wherein R = 3′-t-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl) and the like. (Phenyl) benzotriazole, (ii) 2-hydroxybenzophenone, such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy. 4-dodecyloxy, 4-benzyloxy, 4,2 ',
4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives, (iii) 4-t-butyl-phenyl salicylate; phenyl salicylate; octylphenyl salicylate; dibenzoyl resorcinol; bis (4-t-butylbenzoyl ) Resorcinol; benzoylresorcinol; 2,4-di-t-butylphenyl 3,
5-di-t-butyl-4-hydroxybenzoate; hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate; octadecyl 3,5-di-t-butyl-4-hydroxybenzoate; and 2-methyl- Substituted and unsubstituted benzoic esters such as 4,6-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, (iv) ethyl α-cyano-β, β-diphenyl acrylate; isooctyl α-cyano-
β, β-diphenyl acrylate; methyl α-carbomethoxycinnamate; methyl α-cyano-β-methyl-p-methoxycinnamate; butyl α-cyano-β-methyl-p-
Methoxycinnamate; methyl α-carbomethoxy-p-methoxycinnamate; and acrylates such as N- (p-carbomethoxy-β-cyanovinyl) -2-methylindoline, (v) n-butylamine, triethanolamine or N 1: 1 or 1: 2 complexes with or without additional ligands such as cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; methyl or ethyl ester of 4-hydroxy-3.5-di-t-butylbenzylphosphonic acid Nickel salts of monoalkyl esters containing: 2-hydroxy-4-methylphenylundecyl ketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands Including nickel complexes of ketoximes containing 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol] Nickel compounds such as nickel complexes; (vi) bis (2,2,6.6-tetramethylpiperidin-4-yl) sebacate; bis (2,2,6,6
-Tetramethylpiperidin-4-yl) succinate; bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis (1-octyloxy-2,2,6,6-tetramethyl Piperidin-4-yl) sebacate; bis (1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-t-butyl-4-hydroxybenzylmalonate; 1- Condensate of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; N, N'-bis (2,2,6,6-tetramethylpiperidine-4- Yl) Hexamethylenediamine and 4-t-octylamine-2,6-dichloro-1,3,5-triazine condensate; Tris (2,2
, 6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis (2,
2,6.6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethyl 4-bendiyl-2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis (1,2,2,6,6- (Pentamethylpiperidyl) -2-n-butyl-2-
(2-hydroxy-3,5-di-t-butylbenzyl) malonate; 3-n-octyl-7,7,9,
9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione; bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate; bis (1- Octyloxy-2,2,6,6-tetramethylpiperidyl) succinate; N.N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, Condensate of 6-dichloro-1,3,5-triazine; 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-
Condensation product of tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane; 2-chloro-4 6-bis (4-n-butylamino-1,2, Condensate of 2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane; 8-acetyl-3-dodecyl-7,7,9 , 9-Tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione; 3-dodecyl-1- (2,2,6,6-tetramethylpiperidine
-4-yl) pyrrolidin-2,5-dione; 3-dodecyl-1- (1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione; 3- Dodecyl-1- (1,2,2,6,6
-Pentamethylpiperidin-4-yl) pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; N, N′-bis ( Condensate of 2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; 1,2-bis (3- Aminopropylamino) ethane, a condensate of 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2.2.6,6-tetramethylpiperidine (CAS Reg. No. [136504-96- 6J)
; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxaspiro [
4.5] decane; oxo-piperandinyl-triazine or so-called PIP-T HALS,
For example, GB-A-22698 such as GOODRITER 3034, 3150 and 3159 and similar materials disclosed in US Pat. No. 5,071,981; SANDUVORR PR-31 and PR-32 (Clariant Corp.).
Photocoupled HALS such as similar materials disclosed in 19; and 7,7,9,9-Tetramethyl-2-cycloundecyl-1-oxa-3,8-dioxa-4-oxaspiro [4.5] decane Sterically hindered amines such as the reaction products of epichlorohydrin and N derivatives thereof (e.g.,
N-alkyl, N-hydroxy, N-alkoxy and N-acyl), (also generally U.S. Pat.Nos. 4,619,956, 5,106,891, GB-A-22
(See also 69819, EP-A-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608) (vii) 4,4′-Dioctyloxyoxaanilide; 2,2′-diethoxy Oxaanilide; 2,2'-dioctyloxy-5,5'-di-t-butoxaanilide;2,2'-didodecyloxy-5,5'-di-t-butyloxaanilide; 2-ethoxy-2 ' -Ethyloxaanilide
; N, N'-bis (3-dimethylaminopropyl) oxamide; 2-ethoxy-5-t-butyl
Mixtures with -2'-ethyloxaanilide and 2-ethoxy-2'-ethyl-5,4'-di-t-butoxaanilide; and mixtures of o- and p-methoxydisubstituted oxaanilide and o-
And oxamides such as mixtures of p-ethoxydisubstituted oxaanilides, (viii) 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine; 2- (2-hydroxy-4 -n-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4- (mixed iso-octyloxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine; 2,4-bis (
2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-
Triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4-dodecyloxyphenyl)- Four
, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine; 2-
[2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine; 2- [4-dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3
, 5-triazine; 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl l-4,6-bis (2,4-d [methylphenyl) -1,3,5- Triazine; 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine; 2
-(2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine; 2,4
, 6-Tri-s- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1
, 3,5-triazine; and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-
2- (2-hydroxyphenyl) -1,3,5-triazine disclosed in the previously incorporated citations such as phenyl-1,3,5-triazine, (c) N, N'-diphenyloxamide ; N-salicyral-N'-salicyloylhydrazine;
N, N'-bis (salicyloyl) hydrazine; N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine; 3-salicyloylamino-1,2,4-triazole Bis (benzylidene) oxalyl dihydrazide; oxaanilide; isophthaloyl dihydrazide; sebacoyl bisphenyl hydrazide; N, N'-diacetyladipoyl dihydrazide; Metal activity reducing agents such as bis (salicyloyl) thiopropionyl dihydrazide, (d) triphenyl phosphite; diphenylalkyl phosphite; phenyldialkyl phosphite; tris (nonylphenyl) phosphite; trilauryl phosphite; trioctadecyl phosphite; Distearyl pentaerythritol diphosphite; tris (2,4-di-t-butylphenyl) Sufaito; diisodecyl pentaerythritol diphosphite, bis (2,4, - di -t- butyl phenyl)
Pentaerythritol diphosphite; bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite; bis (isodecyloxy) pentaerythritol diphosphite; bis (2,4-di-t -Butyl-6-methylphenyl) pentaerythritol diphosphite; bis (2.4,6-tris (t-butyl) phenyl) pentaerythritol diphosphite; tristearylsorbitol phosphite; tetrakis (2,4-di-t -Butylphenyl) -4,4'-biphenylenediphosphonite; 6-
Isooctyloxy-2,4,8,10-tetra-t-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphine; 6-fluoro-2,4,8,10 -Tetra-t-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphine; bis (2,4-di-t-butyl-6-methylphenyl) methyl phosphite And phosphites and phosphonite such as bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, (e) N, N-dibenzylhydroxylamine; NN-diethylhydroxylamine; N, N
N-dioctylhydroxylamine; NN-dilaurylhydroxylamine; NN-ditetradecylhydroxylamine; N, N-dihexadecylhydroxylamine; N,
N-dioctadecyl hydroxylamine; N-hexadecyl-N-octadecyl-hydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and hydroxylamines derived from hydrogenated tallow fatty amines, such as N, N-dialkylhydroxylamine, (f) N-benzyl-alpha-phenylnitrone; N-ethyl-alpha-methylnitrone; N-octyl-alpha-heptylnitrone; N-lauryl-alpha-undecylnitrone; N-tetradecyl-alpha-tridecylnitrone; N-hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecyl nitrone; N-hexadecyl-alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl-alpha-heptadecyl nitrone; N
-Octadecyl-alpha-hexadecyl nitrone; and nitrones such as nitrones derived from N, N-dialkylhydroxylamine produced from hydrogenated tallow fatty amine; (g) dilauryl thiodipropionate and distearyl thiodipropionate (H) β-thiodipropionate, such as lauryl, stearyl, myristyl or tridecyl ester; mercaptobenzimidazole or 2-mercaptobenzimidazole zinc salt; zinc dibutyl dithiocarbamate; dioctadecyl disulfide And a peroxide remover such as pentaerythritol tetrakis (β-decylmercapto) propionate; (i) a polyamide stabilizer such as a copper salt in combination with an iodide and / or phosphorus compound and a divalent manganese salt; (j) melamine ; Polyvinyl Loridone; dicyandiimide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyimides; polyurethanes; magnesium,
Basic co-stabilizers such as sodium ricinoleate and potassium palmitate; antimony pyrocatecholate; and tin pyrocatecholate; (k) metal oxides of talc and, preferably, alkaline earth metals (eg, titanium oxide or oxide) Magnesium) and inorganic substances such as phosphates, carbonates and sulfates; organic compounds such as mono- or polycarboxylic acids and their salts, for example, 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate And nucleating agents comprising polymeric compounds such as ionic copolymers (e.g., ionomers); and (l) calcium carbonate; silicates; glass fibers; asbestos; talc; kaolin;
Mica; barium sulfate; metal oxides and hydroxides; carbon black; graphite; wood flour and other natural product powders or fibers; and fillers and reinforcing agents such as synthetic fibers; Other additives such as emulsifiers, pigments, rheological additives, catalysts, leveling aids, optical whitening agents, flame retardants, antistatic agents and foaming agents, (n) U.S. Pat. No. 4,325,863, U.S. Pat. , U.S. Patent 5,175,312,
U.S. Patent No. 5,21 6.052, U.S. Patent No. 5,252,643, DE-A-43 1 661 1, DE-A-43
3-622, DE-A-43 1 6876, EP-A-0589839 and EP-A-0591 102
-(2-acetoxy-ethoxy) phenyl] -5,7-di-t-butyl-benzofuran-2-one; 5
, 7-Di-t-butyl-3- [4- (2-stearoyloxyethoxy) -phenyl] benzofuran-2-one; 3,3'-bis [5,7-di-t-butyl-3- ( 4- [2-hydroxyethoxy]
Phenyl) benzofuran-2-one]; 5,7-di-t-butyl-3- (4-ethoxyphenyl)
Benzofuran-2-one; 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-t-butyl-benzofuran-2-one; 3- (3,5-dimethyl-4-pivalo Yloxyphenyl) -5,
Benzofuranone and indolinone, such as 7-di-t-butyl-benzofuran-2-one; and 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one.

The novel benzo-ring-substituted pyrimidines and triazines of the present invention can also be used in multilayer systems. In such a system, a polymer composition having from about 0.1 to about 20% by weight, preferably a high content of the novel stabilizer, such as about 5-15% by weight, may be a thin film (eg, about 5-500 μm thick, Preferably, it is applied to a molded article made of a polymer having little or no stabilizer (about 10-1OO μm thick). Such a composition may be molded, for example by coextrusion, in a manner similar to that described in U.S. Pat.No. 4,948,666, which is hereby incorporated by reference for all purposes. Coated at the same time. Alternatively, the coating can also be performed on a freshly formed base structure, for example by lamination with a film or by coating with a solution. The outer layer or layer of the finished article has the function of a UV filter that protects the interior of the article from UV light. The outer layer is preferably about
0.1 to about 20%, preferably about 1 to about 15%, most preferably about 2 to about 10% by weight
Of at least one benzo ring-substituted pyrimidine or triazine compound of the present invention.

The polymer stabilized by this method has remarkable high weather resistance, particularly high durability against UV light. This allows these polymers to retain long-lasting mechanical properties and properties of the colored surface, such as gloss and clarity of the image, even when used outdoors.

In addition, due to the binding properties of the triazine compounds claimed in the present invention, migration of these UV absorbers between multilayer coatings can be minimized in a suitable environment.

In another embodiment of the present invention, a novel mixture comprising a compound of formula (1), (II), or (IV)-(IX) is disclosed in a coating, for example, in a number of references. Such paints (e.g., U.S. Pat.No. 4,619,956, U.S. Pat.No. 4,740,542,
U.S. Patent No.4,826,978, U.S. Patent No.4,962,142, U.S. Patent No.5,106,891,
U.S. Patent No.5,198,498, U.S. Patent No.5,298,067, U.S. Patent No.5,322,868,
U.S. Patent No. 5,354,794, U.S. Patent No. 5,369,140, U.S. Patent No. 5,420,204, U.S. Patent No.
3) can be used as stabilizers. Of particular interest are coatings and paints for the automotive industry. Therefore, the present invention also relates to a composition which is a film-forming binder for coating.

Such novel coating compositions may comprise from about 0.01 to about 20%, preferably about 0%.
0.01 to about 10%, more preferably about 0.02 to about 5% by weight of the binder of the benzo ring-substituted pyrimidine and triazine coating compositions claimed herein.

The novel stabilizer concentration in one or more layers, and usually an outer layer such as a clear coat, is relatively high, eg, from about 0.01 to about 20%, preferably from about 0.01 to about 1%.
Multilayer systems are also possible, with 0%, more preferably from about 0.02 to about 5% by weight of the binder (electrocoat / basecoat / clearcoat systems, etc.).

The use of the novel stabilizers in coatings involves peeling the coating from the substrate,
That is, it has the additional advantage of preventing flake separation. This advantage is particularly important for metal substrates, including multilayer systems on metal substrates, especially epoxy coated metal substrates.

The binder may in principle be any binder customary in the industry, for example Ullmann's Encyc] opedia of Industrial Chemi, which is hereby incorporated by reference.
stry, 5th edition, A18, 368-426, VCH, Weinheim 1991. Generally, it is a film-forming binder based on thermoplastic or curable resins, mostly curable resins. Examples of thermoplastic binders include acrylic, polyester, polyurethane and PVC plastisol. Examples of curable binders include functional alkyds, acrylics, polyesters,
Includes phenolic resins, melamine resins, epoxy resins and polyurethane resins and mixtures thereof.

Such a curable binder can be a room temperature curable binder or a thermosetting binder. Further, in some systems, it may be advantageous to add a curing catalyst to the system. Suitable catalysts for accelerating the curing of the binder are, for example, UlImann's Encyclope
dia of Industrial Chemistry, A 1 8, 8, 469, VCH Verlagsgesellschaft, We
described in inheim 1991. Preferred binders include those comprising a functional acrylate resin and a curing agent.

[0181] A wide variety of binders are used in such coating systems. Examples of suitable coating compositions that include a particular binder include, but are not limited to: 1. paints based on room temperature-curable or thermosetting alkyds, acrylates, polyesters, epoxies or melamine resins or mixtures of such resins, if desired with the addition of a curing catalyst, 2. hydroxyl-containing acrylates, polyesters or poly Two-component polyurethane paints based on ether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 3. one-component polyurethanes based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking; Two-component paints based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates, 5. (poly) ketimines and unsaturated acrylate resins or polyesters. Acetoacetate resins or methacrylamide glycolate methyl ester-based and two-component paints, 6. carboxyl - or amino-containing polyacrylates and polyepoxides based the two-component paints, 7. Two-component paints based on acrylate resins containing anhydride groups and polyhydroxy or polyamino components, 8. (poly) oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates; Two-component paints based on isocyanurates or polyisocyanates, 9. two-component paints based on unsaturated polyacrylates and polymalonates, 10. based on externally crosslinkable acrylate resins in combination with thermoplastic acrylate resins or etherified melamine resins 11. A thermoplastic polyacrylate coating, 11. A coating system based on a siloxane-modified or fluorine-modified acrylate resin.

In addition to the binder and the novel benzo ring-substituted pyrimidines and triazines of the present invention, the coating compositions of the present invention preferably include, but are not limited to, one or more, including those specifically listed in section b above. It further comprises a further additional UV absorber. Additional UV absorbers include, for example, another tris-aryl-1
, 3,5-triazine, 2-hydroxyphenyl-2H-benzotriazole, 2-hydroxybenzophenone, unsubstituted benzoate, acrylate, oxaamide (oxaanilide), or any combination of the above. Preferably, additional U
V The absorbent is 2-hydroxyphenyl-2H-benzotriazole, the weight ratio of benzotriazole to triazine is from 4: 1 to 1: 4. More preferably,
The weight ratio is from 2: 1 to 1: 2.

For obtaining the highest photostability, the addition of sterically hindered amines as exemplified in section b (vi) above is of particular interest. Therefore, the present invention also provides a coating composition comprising, in addition to a binder, the novel benzo-substituted pyrimidines and triazines and optionally an additional UV absorber, a light stabilizer in the form of a sterically hindered amine. About things. Sterically hindered amines comprise about 0.01 to 5% by weight, based on the weight of the solid binder,
Preferably it is used in an amount of about 0.02 to 2% by weight.

A particular example of such a sterically hindered amine is represented by the formula

[0185]

Embedded image

(In the formula, J is, for example, hydrogen, hydroxyl, alkyl (methyl or the like), alkoxy (
2,2.6,6-tetramethylpiperazinone containing at least one group of

More preferably, the stabilizer has the formula

[0188]

Embedded image

(In the formula, J is, for example, hydrogen, hydroxyl, alkyl (methyl or the like), alkoxy (
2,2.6,6-tetraalkylpiperazine derivatives comprising at least one group of the formula:
Examples of tetraalkylpiperidine derivatives that can be used in combination with the trisaryl-1,3,5-triazine compounds of the present invention are described in U.S. Pat. , 3 1 4,933, 4,344,876, 4th
No., 426,471, No.4,426,472, No.4.61 9,956, No.5.004,770, No.5,006,577, No.5,064,883, No.5,112,890, No.5,124,378, No.5,106,891, No.5,204,47
No. 3, and No. 5,461,151. The following tetraalkylpiperidine derivatives
, And their N-alkyl, N-acyl, N-hydroxyl and N-alkoxy analogs (which are then not already encapsulated). Screw (2,2,6,6
-Tetramethylpiperidi-4-yl) succinate, bis (2,2,6,6-tetramethylpiperidi-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidi- 4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperidi-4-yl) butyl- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis (1 -Octyloxy-7-, 2,6,6-tetramethylperidi-4-yl) sebacatetetra (2,2,6,6-tetramethylperidi-4-yl) butane-1,2,3,4 -Tetracarboxylate, tetra (1,2,2,6,6-pentamethylperidi-4-yl) butane-1,2,3,4-tetracarboxylate, 2,2,4,4-tetramethyl- 7-oxa-3,20-diaza-21-oxo-dispiro [5,1,11,2] henicosane and 8-acetyl-3-dodecyl-1,3, g-triaza-7,7,9, 9-tetramethylspiro [4 ・
5] Decane-2,4-dione. Commercially available examples of these and other tetraalkyl piperidine derivatives, SANDUVOR ^R 3050,3052,3055,3056,3058, PR-31 and PR-3
2 (Clariant Corp.); TINUVIN ^R 079L, 123, 144, 292, 440L and 622LD (Ciba S
pecialty Chemicals); CHIMASORB ^R 119 and 944 (Ciba Specialty Chemicals);
And CYASORB ^R UV-3346, UV 3529, UV-3853, UV-500 and UV-516 (Cytec Indust
ries Inc.).

Apart from the binder benzo-substituted pyrimidines or triazines and, if used, additional UV absorbers or stabilizers, the coating composition may also comprise further components. Examples are solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, dry catalysts and / or leveling agents.
Examples of possible ingredients are found in the numerous references cited earlier, as well as in Ullmann's Encyclopedia.
of Industrial Chemistry, 5th edition, Al 8, 429-471, VCH, Weinheim 1 991;
And Calbo, Leonard J., Ed., Handbook of Coatings Additives, New York: Marcel
It is described in Dekker (1987).

Possible drying or curing catalysts are, for example, organometallic compounds, amines, acids, amino-containing resins and / or phosphines.

Examples of acid catalysts include mineral acids, aliphatic and aromatic sulfonic acids (eg, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid), oxalic acid, maleic acid, hexamic acid, phosphorus Acids, alkyl phosphates, phthalic acid and acrylic acid copolymers.

Examples of organometallic compounds are metal carboxylates, especially metals Pb, Mn, Co, Zn, Z
r or Cu carboxylate or metal chelate, especially metal Al, It or Zr
Or an organic metal compound such as an organic tin compound. Examples of metal carboxylates are stearate of Pb, Mn or Zn, octoate of Co, Zn or Cu, naphthenate of Mn and Co or the corresponding linoleate, resinate or tartrate. Examples of metal chelates are aluminum, titanium or zirconium chelates of acetylacetone, ethylacetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetone or ethyltrifluoroacetylacetate, and alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.

Examples of amine drying or curing catalysts are, in particular, tertiary amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diamine. Zabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride. Amino-containing resins are simultaneously a binder and a curing catalyst. Examples of these are amino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for example triphenylphosphine.

Another type of curing catalyst is a peroxide used to cure gel coatings for glass fiber articles.

The novel coating composition can also be a radiation-curable coating composition. In this case, the binder basically comprises a monomer or oligomeric compound containing an ethylenically unsaturated bond, which after application is cured by actinic radiation, ie converted into a crosslinked high molecular weight form. If the system is UV-curable, it generally contains a photoinitiator. The corresponding system is Ullmann's Encycloped from the above publication.
ia of Industrial Chemistry, 5th edition, A1, Vol. 8, pages 451-453. In radiation-curable coating compositions, the novel stabilizers can also be used without the addition of sterically hindered amines.

The novel coating composition according to the present invention can be applied to any desired substrate, such as a metal,
It can be applied to wood, plastic, glass fiber or ceramic materials. The coating composition can be a pigmented mono-coat or a multilayer system typical for automotive finishes (primer / basecoat / clearcoat). In the latter case, the novel coating composition can be used for the basecoat or clearcoat, or for both layers. Top coat of car finish 2
If the coating composition consists of layers, the lower layer is pigmented and the upper layer is not added, the novel coating composition can be used for the upper or lower layer, or for both layers, but preferably the upper Used for layers.

The novel coating compositions can be applied in a customary manner, for example by brushing, spraying, pouring, dipping or electrophoresis. Ullmann's Encyclopedia of
See also Industrial Chemistry, 5th Edition, Al8, pp. 491-500.

Depending on the binder system, the coating can be cured at room temperature or by heating. Thermosetting coatings are preferably cured at 50-150 ° C. and, in the case of powder coatings, at even higher temperatures.

The coatings obtained according to the invention have excellent resistance to light, oxygen and heat damage. The good light stability and weatherability of the coatings thus obtained, such as paints, are particularly noteworthy.

The present invention therefore also relates to the presence of the compounds according to the invention of the formula (1), (II) or (IV)-(X), whereby the compounds are protected against the damaging effects of light, oxygen and heat. It relates to stabilized coatings, especially paints. The coating can be a pigmented monocoat comprising a film-forming binder and an organic or dye, inorganic pigment, metal pigment, or a mixture thereof. The paint may also be a primer that adheres to a metal or plastic substrate, a pigmented base coat that adheres to the primer and comprises a film-forming binder and an organic or dye, inorganic, metallic, or mixture thereof. And a clear coat that adheres to the base coat and comprises a film-forming binder and optionally a transparent pigment. One particularly preferred use is for paints that are clear topcoats for automotive OEM and / or refinishing applications.

Further, the present invention provides that a polymer-based coating comprising mixing a coating composition and a mixture comprising a benzo-ring-substituted pyrimidine or triazine compound is protected from light, oxygen and / or heat damage. A method for stabilizing against light, oxygen and / or heat damage to a coating composition comprising a mixture comprising a benzo ring-substituted pyrimidine or triazine compound as a stabilizer against light, oxygen and / or heat damage.

[0205] The coating composition comprises an organic solvent or solvent mixture in which the binder is soluble. Otherwise, the coating composition can be an aqueous solution or dispersion. The vehicle can also be a mixture of an organic solvent and water. The coating composition may be a high solids paint, or
It can be solventless (eg, a powder coating material).

The pigment can be an inorganic, organic or metallic pigment. The novel coating composition is preferably free of pigments and is used as a clearcoat.

Also preferred is the use of the coating composition as an automotive topcoat.
In particular, it is used as a top coat with or without the addition of a pigment for paint finish. However, use for a base coat is also possible.

The benzo-ring-substituted pyrimidines or triazines of the invention comprise a benzo-ring-substituted pyrimidine or triazine and a solvent, vaseline, a silicone oil-in-water emulsion, or an inert carrier such as an automotive paint wax, eg, carnauba wax. The surface is coated by polishing the surface with the composition. These surface treatment compositions are used to stabilize coating films, fabrics, leather, vinyl and other plastics and wood.

In photographic materials, it is also preferred to use the novel benzo-substituted pyrimidine or triazine compounds as stabilizers against damage by light, in particular UV light. Therefore, the present invention also relates to a photographic material containing a benzo ring-substituted pyrimidine or triazine compound.

The compounds according to the invention can be used for all types of photosensitive materials. For example,
These can be used for color paper, color reversal paper, direct positive color materials, color negative films, color positive films, color reversal films and other materials. These are preferably used, inter alia, for photosensitive color materials which contain reversal substrates or which form positives.

In addition, the novel compounds can be used with other UV absorbers, especially those that can be dispersed in aqueous gelatin, such as hydroxyphenylbenzotriazole (see, eg, US Pat.
No. 853,471, 5,4973,702, 4,921,966 and 4,973,701), benzophenone, oxaanilide, cyanoacrylate, salicylate, or acrylonitrile or thiazoline. In this context,
It is advantageous to use these additional oil-dispersed UV absorbers in photographic materials in layers other than those comprising the novel UV absorber.

[0212] The present invention also encompasses compositions containing one or more binders. In particular, the binder comprises an alkyd resin, an acrylic resin, a polyester resin, a phenolic resin, a melamine resin, an epoxy resin or a polyurethane resin, or a blend thereof. Examples of these binders include, but are not limited to: (a) cold- or hot-crosslinkable alkyd resin, acrylate resin, polyester resin, epoxy resin or melamine resin or a mixture of these resins; (b) hydroxyl-containing acrylate, polyester or polyether resin and aliphatic or aromatic Two-component polyurethane systems comprising isocyanates, isocyanurates or polyisocyanates; (c) one-component polyurethanes based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking; (d) (poly) ketimines; One-component systems comprising aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; (e) (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or methacrylamides A component system comprising cholate methyl ester; (f) a binary system comprising carboxyl- or amino-containing polyacrylates and polyepoxides; (g) comprising an acrylate resin containing anhydride groups and a polyhydroxy or polyamino component. Two-component systems, (h) two-component systems comprising (poly) oxazoline and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates, (i) (J) a thermoplastic polyacrylate layer comprising an externally crosslinkable acrylate resin in combination with a thermoplastic acrylate resin or an etherified melamine resin, (k) siloxane modified or fluorine Modified acrylate System comprising fat. Such a binder-containing composition further contains a curing catalyst or an organic solvent, and is radiation-crosslinkable. In particular, such compositions function as coating compositions.

In particular, photosensitive materials similar to those described in US Pat. No. 4,518,686 can be successfully stabilized.

Therefore, in addition, the present invention comprises, on a support, a blue-sensitive, green-sensitive and / or red-sensitive silver halide emulsion layer and, if desired, a protective layer,
The present invention relates to a light-sensitive material in which a layer comprising a UV absorber is disposed on the uppermost layer of the halide emulsion, and the UV absorber is a benzo ring-substituted pyrimidine or triazine compound.

In addition, on top of the silver halide emulsion top layer and / or between the green and red photosensitive silver halide emulsion layers, the compounds of formula (1), (Il) or (IV)-(IX) A photosensitive material having a layer containing

In addition, it is advantageous that all or part of the above-mentioned layers, which can comprise UV absorbers, have an aqueous gelatin-dispersible UV absorber mixture and / or further UV absorbers, The compounds of the formula (1), (Il) or (IV)-(IX) used according to the invention must be present in at least one layer.

The novel material preferably has a gelatin interlayer between the silver halide emulsion layers.

The silver halide in the blue-sensitive, green-sensitive and / or red-sensitive layers is preferably a silver chlorobromide photosensitive material containing at least 90 mol% of silver chloride.

By dissolving this compound in advance in a high boiling organic solvent, the compound of formula (1), (II) or (IV)-(IX) used according to the invention can be used alone or in a color coupler and If necessary, they can be included in the color photographic material together with further additives. It is preferable to use a solvent that boils above 160 ° C. Typical examples of such solvents are phthalic, phosphoric, citric, benzoic or fatty acid esters, or alkylamides and phenols.

Preferred color couplers for use in the compositions of the present invention, examples of such compounds, further additives such as color cast inhibitors,
IR coupler, UV absorber, phenol, phosphorus (III) compound, organometallic complex,
Further light stabilizers, such as hydroquinone and hydroquinone ethers, and more precise details on the structure of various photographic materials are described, for example, in publications EP-A-053 1258 and
It is found in EP-A-0520938 and the references cited therein.

[0221] Film The invention also agricultural use, in particular to a method of stabilizing a polyolefin or polyolefin copolymer films for greenhouses, this polyolefin or polyolefin copolymer film, at least one of the benzo ring of the present invention - substituted pyrimidine or triazine UV Absorbent, sterically hindered amine and zinc, aluminum,
A metal oxide selected from oxides of calcium and magnesium and hydroxides of zinc, aluminum and calcium, including a hydroxide in the polyolefin or polyolefin copolymer to provide improved light stability and Has insecticide resistance.

A further subject matter of the present invention is that at least one benzo-substituted pyrimidine or triazine UV absorber according to the invention, having improved photostability and insecticide resistance, a sterically hindered amine and zinc, aluminum , Calcium and magnesium oxides and metal oxides selected from zinc, aluminum and calcium hydroxides,
A greenhouse characterized by being covered by a polyolefin or polyolefin copolymer film stabilized by a hydroxide.

Another subject of the present invention is a method for stabilizing polyolefin or polyolefin copolymer greenhouse films against pesticides and the detrimental effects of light, oxygen and / or heat, comprising at least one benzo-ring of the present invention. Substituted pyrimidine or triazine UV absorbers, sterically hindered amines and oxides of zinc, aluminum, calcium and magnesium and metal oxides and hydroxides selected from zinc, aluminum and calcium hydroxides in the greenhouse film A method comprising including.

A further subject of the invention is at least one benzo-substituted pyrimidine of the invention for stabilizing a polyolefin or polyolefin copolymer film in contact with the insecticide against photolysis and damage by the insecticide. Triazine UV absorbers, sterically hindered amines and oxides of zinc, aluminum, calcium, and magnesium and metal oxides selected from the hydroxides of zinc, aluminum, and calcium, and polyolefin copolymer films stabilized by hydroxides Is to use.

To form a film, an amount of the molten composition is extruded from a film die, such as a flat die or an annular blow die, and then a film is formed.
When the composition is used to form a film, the film may be unoriented or subjected to conventional operations to impart some degree of film orientation. Such films may be oriented in one direction, such as "machine direction" and / or "width direction", or they may be oriented in two directions, i.e., "biaxial".

The present invention is also suitable for sheet applications. Benzo ring-substituted pyrimidine or triazine compounds of formulas (1), (ll) and (IV)-(IX) are, for example, silk, hide, wool,
Suitable for light stabilization of undyed, dyed or printed fibrous materials, including polyamides or polyurethanes and especially all types of cellulose-containing fibrous materials. Examples of such fibrous materials are cotton, linen, jute and hemp and also natural cellulose fibers such as viscose staple fibers and regenerated cellulose. Preferred textile fiber materials are cotton materials. The benzo-ring-substituted pyrimidine or triazine compounds of the present invention are also suitable for light stabilizing blended fibers, for example, hydroxyl-containing fibers of cotton and polyester fibers or polyamide fiber blends. Further preferred areas of application relate to the blocking or reduction (UV cutting) of UV light passing through the above-mentioned textile materials and the enhanced sun protection provided by the novel textile finished textile materials to the human skin.

For this purpose, one or a number of different compounds of the formula (1), (II) or (1V)-(IX) are converted by one of the customary dyeing methods, based on the weight of the fiber material. , 0.01-5% by weight
Advantageously, it is applied to the textile fiber material in an amount of preferably 0.1 to 3% by weight, in particular 0.25 to 2% by weight.

The benzo-ring-substituted pyrimidine or triazine compounds are applied to the fiber material in the form of aqueous dispersions or printed glues by various methods and are fixed to the fibers.

Textile fiber materials finished with the novel compounds of the formulas (1), (II) or (IV)-(IX) have improved protection against fiber photochemical degradation and yellowing phenomena ,
In the case of dyed fiber materials, light fastness is increased. The greatly improved light protection effect of the treated textile fiber material and the good protection effect, especially with respect to short wavelength UV-B radiation, is particularly emphasized. This is indicated by the fact that textile fiber materials finished with benzo-ring-substituted pyrimidine or triazine compounds have an increased sun protection factor (SPF) compared to untreated fabrics.

The sun protection factor is defined as the ratio of the amount of protective skin damage to the amount of UV light that damages unprotected skin. Thus, the sun protection factor also depends on the extent to which the fiber material treated with the novel compound of formula (I), (II) or (IV)-(IX) relative to the untreated fiber material is transparent to UV light. It is a guide. The definition of the sun protection factor for textile fiber materials is, for example, W094 / 045 15 or J
Soc. Cosmet. Chem. 40, 127-133 (1989) and can be practiced similarly.

Yet another use of UV absorbers according to the invention is for the stabilization of intraocular and contact lenses. The UV absorbers of the present invention are suitable as photoprotective agents in cosmetic formulations. Therefore, the present invention additionally relates to a cosmetic formulation comprising at least one benzo-ring-substituted pyrimidine or triazine compound and a cosmetically acceptable carrier or adjuvant.

The novel cosmetic compositions comprise, on a total weight basis, from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, of a benzo-substituted pyrimidine or triazine UV absorber and a cosmetically acceptable auxiliary. contains.

The cosmetic compositions can be manufactured in a customary manner, for example by physically mixing the novel UV absorber with the auxiliaries by stirring the two materials together.

The cosmetic preparations according to the invention can be prepared as water-in-oil or oil-in-water emulsions, as alcoholic lotions of oil-in-oil, as vesicular dispersions of ionic or non-ionic amphoteric lipids, as gels, solid sticks, Alternatively, they may be formulated as an aerosol formulation.

As oil-in-water or water-in-oil emulsions, cosmetically acceptable auxiliaries preferably contain 5 to 50% of an oil phase, 5 to 20% of an emulsifier, and 30 to 90% of water. The oily phase can comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, waxes, natural oils, silicone oils, fatty acid esters or fatty alcohols. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.

For these cosmetic formulations, any of the conventional emulsifiers, for example ethoxylated esters of one or more naturally occurring derivatives, ie polyethoxylated esters of hydrogenated castor oil, or silicone It is possible to use silicone oil emulsifiers such as polyols, unmodified or ethoxylated fatty acid soaps, ethoxylated fatty alcohols; unmodified or ethoxylated sorbitan esters, ethoxylated fatty acids or ethoxylated glycerides.

The cosmetic formulation may also comprise further ingredients such as emollients, emulsion stabilizers, skin humectants, sunburn enhancers, thickeners such as xanthan, humectants such as glycerol, preservatives or fragrances and Colorants can also be included.

The novel cosmetic formulations are notable for providing reliable tanning of the skin, while at the same time providing good protection of human skin against the damaging effects of sunlight.

The invention is illustrated by the following example. This example is not intended to limit the scope of the present invention. The examples, in conjunction with the general and detailed description above, provide a further understanding of the present invention.

EXAMPLES Examples and reaction schemes for preparing specific examples of benzo-ring-substituted triazines according to the present invention are provided below. The following examples illustrate the preparation with one or more tetralin benzo rings, but those skilled in the art will appreciate that these reactions can be performed with any of a variety of other benzo rings, in which case, if necessary, It will be appreciated that reactive substituents on other benzo rings are protected by well known methods and reagents known to those skilled in the art.

Synthesis Examples Example 1: Reaction of cyanuric chloride with tetralin: tetralin as solvent
Use of

[0242]

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To a reaction flask equipped with a reflux condenser, an argon inlet, a magnetic stirring bar, and a glass stopper, 100 mL of tetralin and 9.2 g of cyanuric chloride were added. To the resulting solution was added 10 g of anhydrous AlCl ₃ at 0 ° C. for 10 minutes. After the addition was over, the reaction mixture was heated in an oil bath at 40 ° C. for 16 hours. The heat was turned off and the reaction mixture was cooled in an ice bath and treated with ice-cold water. Next, the reaction mixture was extracted with methylene chloride, and the organic layer was dried over anhydrous sodium sulfate and concentrated to remove volatiles. The residue was treated with methanol to give a precipitate, which was filtered, washed with methanol and dried to give 12.4 g of product. By NMR and mass spectrometry of the product,
Monotetralin-bischloro-triazine (Compound A), bistetralin-monochloro-triazine (Compound B) and tristetralin-triazine (Compound C) were shown.

Example 1 Alternative: Use of Monochlorobenzene as Solvent 47.7 g (0.256 mol) of cyanuric chloride and 67.6 g (0
.507 mol) of aluminum chloride was heated to 40 ° C. under nitrogen. Tetralin (
(68 mL, 0.500 mol) was added over 2 hours. During this time, the temperature rose to 50 ° C. The temperature was maintained at 50 ° C. until an exotherm occurred.

After the exotherm subsided, 200 mL of a 10% aqueous HCl solution was added dropwise while maintaining the temperature below 50 ° C. The resulting mixture was filtered. The aqueous phase of the filtrate was extracted with methylene chloride. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate and treated with activated carbon. After filtration, the filtrate was concentrated in vacuo. The residue was dissolved in 300 mL of tetrahydrofuran and cooled to 0 ° C. The precipitate was removed by filtration. The filtrate was concentrated in vacuo to give an oil that slowly crystallized to a dark yellow to brown solid, which was P-40
It contained tristetralin and unreacted cyanuric chloride in addition to 36 (50-70 area% by HPLC).

Example 2 Bistetralin-monoresorcinol-triazine (Compound D)

[0247]

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132.3 g of the product of Example 1 Alternative (Compound B) and 38.7 g in 300 mL of chlorobenzene
A mixture of g resorcinol was heated to 60 ° C. Aluminum chloride (61.0g)
Addition over time, during which time the temperature rose to 80 ° C. The temperature was maintained at 80 ° C. for a further 2 hours.

After cooling to 60 ° C., the reaction mixture was poured into 400 mL of ice water. The mixture was concentrated in vacuo. The residue was ground with 400 mL of water and the resulting slurry was filtered. The solid was air dried and then dried in vacuo. Soxhlet extraction of the solid was performed with refluxing chloroform. A solid precipitated from the chloroform extract. The solid was filtered, washed with cold chloroform and dried to give compound D as a pale yellow powder with> 92% purity by HPLC.

Example 3: Bistetralin-monoresorcinol 4-O-octyl) -triazine
Conductor (Compound E)

[0251]

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A mixture of 400 mg of the product of Example 2 (Compound D), 1.38 g of anhydrous potassium carbonate, 0.2 mL of iodooctane and 10 mL of acetone was heated to reflux for 24 hours. Then the reaction mixture was cooled to room temperature and diluted with methylene chloride. The obtained mixture was filtered through celite, concentrated and dried to obtain 422 mg of a crude product. The crude product was purified by column chromatography on silica gel to give a pure product identified by NMR as a bistetralin-monoresorcinol 4-O-octyl) -triazine derivative (Compound E).

Example 4: Monotetralin-bisresorcinol-triazine derivative (compound G
)

[0254]

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A three-necked 250 mL round bottom flask was charged with 14.0 g of monotetralin-bischloro-triazine derivative (Compound F), 11.56 g of resorcinol and 130 mL of chlorobenzene, and then purged with nitrogen. The solid addition funnel was charged with 18.76 g of anhydrous aluminum chloride. The solution was heated to 49 ° C. and the addition of aluminum chloride was started in portions. Aluminum chloride was added over 2 hours and the temperature slowly increased to 65 ° C. next,
The reaction mixture was heated to 90-95 ° C and kept there for 3 hours. At this point, the mixture was a dark red slurry.

At the end of the reaction period, the heat was removed and the temperature was reduced to about 60 ° C. Next, the accessories were removed from the reaction flask and the reaction mixture was poured into 200 mL of cold water. The mixture was shaken to decolor the red color, yielding a yellow emulsion. After cooling completely, it was transferred to a round bottom flask and the chlorobenzene-water azeotrope was removed on a rotary evaporator until no more chlorobenzene was found in the condensate. The resulting pale yellow slurry was filtered, washed with water, and dried in vacuo to give the desired product (Compound G).

Example 5: Preparation of compounds H and I

[0258]

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4.27 g of compound G, 5.28 g of 1-iodooctane, 6.9 g of anhydrous potassium carbonate, 0.5 g
Of Aliquat and 50 mL of acetone was heated to reflux for 20 hours.
At this stage, add an additional 1 mL of iodooctane and 3.5 g of anhydrous potassium carbonate,
Reflux was continued for another 8 hours. At this stage, TLC analysis showed that Compound G had almost completely disappeared and two new products had been formed. The reaction mixture was cooled to room temperature, diluted with methylene chloride and filtered through celite. The filtrate was concentrated under reduced pressure to give a crude product consisting of compounds H and I analyzed by NMR and mass spectroscopy.
This mixture can be separated on silica gel by column chromatography.

Example 6 Bistetralin-monoresorcinol-triazine 4- (2-hydroxy
Production of (ethyl) ether (compound J)

[0261]

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10.0 g of bistetralin-monoresorcinol-triazine (compound D), 130 m of D
A mixture of MF, 2.6 g of anhydrous potassium carbonate, 0.25 g of potassium iodide, 0.88 g of PEG-400 (polyethylene glycol) and 7.5 g of 2-chloroethanol was heated at 120 ° C. for 15 hours. After the first 9 hours, an additional 2.5 g of 2-chloroethanol was added and heating continued. After the reaction was completed, the reaction mixture was poured into 300 mL of ice water. The precipitated solid was filtered, washed with water and dried. NMR and mass spectrometry indicated that compound J was obtained in> 90% purity.

Example 7 Bistetralin-monoresorcinol-triazine of 4- (6-hydroxy
Production of (ethyl) ether (compound K)

[0264]

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10 g of bistetralin-monoresorcinol-triazine (Compound D, 0.02 mol) and 80 m of MIBK were heated to 90 ° C. 1.0 g (0.031 mol) of sodium hydroxide was slowly added to obtain an almost clear solution. Next, 0.25 g (0.0015 mol) of potassium iodide, 0
.88 g of PEG-400 (polyethylene glycol, approximately 0.0022 mol) was added. After the solution was clear again, 5.7 g (0.031 mol) of 6-chlorohexanol was added.
The mixture was heated at 107-111 ° C for 18 hours. Then the mixture was washed with 1N HCl and water. The resulting solution was dried over magnesium sulfate, filtered, and cooled to 0 ° C. The resulting pale yellow solid was filtered and dried. Compound K> 90% by NMR and mass spectrometry
Was obtained with a purity of.

Example 8: 4-Lauroylue of bistetralin-monoresorcinol-triazine
Manufacture of steal (compound L)

[0267]

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To a mixture of 20 g of compound D and 80 m of ortho-dichlorobenzene was added 11.0 mL of lauroyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture was heated at 150 ° C. for 9 hours. Next, the mixture was cooled to 100 ° C. and 200 mL of ethanol was added. The resulting precipitate was filtered, washed with ethanol, and air dried to give 21.3 g of compound L as a pale yellow solid.

This solid was dissolved in 50 mL of hot toluene. The slurry was warmed in a water bath until all solids were dissolved. Methanol (300 mL) was added to the mixture maintained at reflux temperature. Next, the solution was cooled to room temperature. The resulting solid was filtered, washed several times with methanol and dried in vacuo to give 20.25 g of the title compound as a pale yellow solid.

Example 9 Bistetralin-monoresorcinol-triazine 4-hexanoyl
Production of ester (compound M)

[0271]

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To a mixture of 20 g of compound D and 80 m of orthodichlorobenzene was added 8 mL of hexanoyl chloride (Aldrich) and 10 mL of orthodichlorobenzene. The stirred mixture was heated at 150 ° C. for 12.5 hours. The product was isolated by the procedure of Example 9 to give 14.1 g of compound M as a pale yellow solid.

Example 10 Bistetralin-monoresorcinol-triazine 4-octanoyl
Production of ester (compound N)

[0274]

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To a mixture of 20 g of compound D and 80 m of ortho-dichlorobenzene was added 8 mL of octanoyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture was heated at 150 ° C. for 23.5 hours. The product was isolated by the procedure of Example 2 to give 17.8 g of compound N as a pale yellow solid.

Example 11: 4- (2-ethyl) bistetralin-monoresorcinol-triazine
Production of hexanoyl ester (Compound O)

[0277]

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To a mixture of 20 g of compound D and 80 m of orthodichlorobenzene was added 8 mL of 4- (2-ethylhexanoyl chloride (Aldrich) and 10 mL of orthodichlorobenzene, and the stirred mixture was stirred at 150 ° C. for 20 hours. The mixture was then cooled to 100 ° C. and 200 mL of ethanol was added, and cooled at 0 ° C. overnight, whereupon an oil precipitated.
The supernatant was removed by decantation. The oil was dissolved in a refluxing hexane-toluene mixture and then cooled to 0 ° C. The resulting solid was filtered, washed with methanol, and air-dried to give 21.4 g of a pale yellow solid. This solid was recrystallized from hexane-toluene, washed with methanol and dried in vacuo to give 15.8 g of compound O as a pale yellow solid.
I got

Example 12: Bistetralin-monoresorcinol-triazine 4- (3,5,5-to
Production of Limethylhexanoyl Ester (Compound P)

[0280]

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To a mixture of 20 g of compound D and 80 m of orthodichlorobenzene was added 9 mL of 3,5,5-trimethylhexanoyl chloride (Aldrich) and 10 mL of orthodichlorobenzene. The stirred mixture was heated at 150 ° C. for 7 hours. Next, the mixture was cooled to 100 ° C. and 200 mL of ethanol was added. Upon cooling at 0 ° C. overnight, an oil precipitated. The supernatant was removed by decantation. The oil was washed with 150 mL portions of methanol and dried in vacuo. The obtained glass was recrystallized twice from hexane,
13.1 g of compound P was obtained as a pale yellow solid.

Example 13: 2- (2-hydroxy-4-ethoxycarbonylmethoxyphenyl) -4
Of 2,6-bis (tetralin) -1,3,5-triazine (compound Q)

[0283]

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To a mixture of 9 g of compound D, 6.9 g of anhydrous potassium carbonate, 0.3 g of potassium iodide and 50 mL of acetone, 2.4 mL (2.7 g) of ethyl chloroacetate was added. The mixture was stirred at reflux for 6 hours. HPLC analysis indicated that compound D was completely converted. After cooling, the mixture was diluted with 100 mL of methylene chloride and filtered over a diatomaceous bed, which was washed with an additional 50 mL of methylene chloride. The combined filtrate was concentrated in vacuo. The product was recrystallized from ethyl acetate, dried in vacuo, 8.4 g
Was obtained as a near white solid with a purity of 94% (HPLC area% at 290 nm).
The structure was confirmed by ¹³ C and ¹ H-NMR.

Example 14: 2- [2-hydroxy-4- (N- (n-butyl) -N- (2-hydroxyethyl)-(meth)
Tanamidooxy) phenyl] -4,6-bis (tetralin) -1,3,5-triazine (
Preparation of compound R)

[0286]

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5 g of compound Q, 1.66 g of butylethanolamine, 0.12 g of 4-dimethylaminopyridine and 30 mL of xylene were stirred at reflux. After 26 hours, 2 g of butylethanolamine was added. After 48 hours, HPLC analysis showed 99.5% of compound P had been converted (HPLC area% at 290 nm). The mixture was cooled. 175 mL of precipitated solid
In hexane and stirred for 3 hours. The mixture was filtered and the collected solid was air-dried. The solid was stirred with 150 mL of methanol for several hours, washed with methanol and dried in vacuo to give 5 g of compound R as a white solid with 96% purity (HPLC area% at 290 nm). The structure was confirmed by ¹³ C and ¹ H-NMR.

Example 15 Bistetralin-monoresorcinol -triazine 4-O-propane
Production of sulfonate ester (Compound S)

[0289]

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11.6 g of compound D, 9 g of anhydrous potassium carbonate and 100 mL of tetrahydrofuran (THF)
To a stirred and cooled mixture at 0 ° C. was added 3.15 m in 100 mL of tetrahydrofuran (THF).
A solution of L propanesulfonyl chloride was added over 22 minutes. The resulting mixture was stirred at room temperature for 40 hours. An additional 1 mL of propanesulfonyl chloride was added and the mixture was stirred for 24 hours. HPLC analysis indicated complete conversion of the starting material. The solid was removed by filtration and the product crystallized from the filtrate. The filtered solid was extracted with chloroform and the chloroform was removed in vacuo to give the addition product. The combined yield was 8.5 g. Compound S was obtained by recrystallization from ethyl acetate with a purity of 99% as determined by HPLC (area% at 290 nm). Structure ^13C
And ¹ H-NMR.

Example 16: 4-O-phenyl of bistetralin-monoresorcinol-triazine
Production of sulfonate ester (Compound T)

[0292]

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15 g of compound D, 13.8 g of anhydrous potassium carbonate and 100 mL of tetrahydrofuran
To the cooled mixture was added a solution of 5.2 mL (7.1 g) of benzenesulfonyl chloride in 30 mL of THF over 37 minutes. The resulting mixture was warmed to room temperature and stirred for 19 hours. An additional 1 mL of benzenesulfonyl chloride was added and the mixture was stirred for 3 hours. Methanol (5 mL) was added. The mixture was filtered and the solid was washed with THF. The product was recrystallized from the combined filtrates, filtered and dried. Compound T (11.3 g) was obtained as a white solid by recrystallization from chloroform / hexane (1: 3 v / v). HPLC analysis showed 99% purity (area% at 290 nm). The structure was confirmed by ¹³ C and ¹ H-NMR.

Example 17: Monotetralin-monoresorcinol-monochloro-1,3,5-tria
Gin (Compound U)

[0295]

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To a stirred mixture of 2.8 g of monotetralin-bischloro-1,3,5-triazine (Compound F), 1 g of resorcinol and 25 mL of chlorobenzene, 1.34 g of aluminum chloride was added at ice bath temperature. The reaction mixture was warmed to 15 ° C. and stirred for 3 hours. The reaction mixture was warmed to room temperature and stirred for 20 hours. The reaction mixture was quenched with ice-cold aqueous hydrochloric acid. A precipitate formed, which was collected by filtration, washed with water and dried. The precipitate was analyzed by thin layer chromatography (TLC), HPLC, and mass spectrometry to identify compound U as the major product.

Example 18 Bistetralin-monoresorcinol-1,3,5-triazine hinder
Production of phenol adduct (compound V)

[0298]

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To a stirred mixture of 2.25 g of compound D, 2.76 g of anhydrous potassium carbonate and 150 mL of acetone, 1.24 g of 3-chloromethyl-2,4-dimethyl-6-t-butylphenol, 150 mg of sodium iodide and 250 mg Aliquat ^R 336 (triscapril methyl ammonium chloride) was added. The reaction mixture was heated to reflux for 3 hours. No starting material was detected by TLC and HPLC analysis, and only one major product was detected. The reaction mixture was cooled to room temperature, diluted with 50 mL of methylene chloride, and filtered through Celite ^R brand filter agent. The filtrate was concentrated under reduced pressure. The residue was dissolved in 100 mL of methylene chloride, dried over anhydrous sodium sulfate, concentrated and dried,
Analysis by mass spectrometry gave compound V.

Example 19: Hindered monotetralin-bisresorcinol-1,3,5-triazine
Production of phenol adducts (compounds W and X)

[0301]

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To a stirred mixture of 2.14 g of compound G, 5.5 g of anhydrous potassium carbonate, and 40 mL of MIBK,
3-chloro-2,4-dimethyl -6-t-butylphenol 2.49 g, was added Arikuwatto ^R 336 sodium iodide and 250mg of 150 mg. The reaction mixture was heated to reflux for 8 hours. After 8 hours, little starting material was detected by TLC analysis. The reaction mixture was cooled to room temperature, diluted with methylene chloride and filtered through Celite ^R brand filter agent. The filtrate was concentrated under reduced pressure and analyzed by TLC to give a mixture of compounds W and X Example 20: 2,4-bis (tetralin) -6- (2,4-hydroxy-3-diallylamino
Production of (methyl) -1,3,5-triazine (compound Y)

[0303]

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To a stirred suspension of 2.25 g of compound D in 50 mL of toluene was added 3 mL of diallylamine and 5 mL of an aqueous formaldehyde solution. The reaction mixture was heated to reflux for 4 hours. After 4 hours, little starting material was detected by TLC analysis, indicating the formation of one major product. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. 100 mL of residue
Was washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and analyzed by mass spectrometry to give compound X.

Example 21 Bistetralin-monoresorcinol-1,3,5-triazine dimer
Production of (Compound Z)

[0306]

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10 g of compound D, 12.2 g of anhydrous potassium carbonate, 3.9 g of 1,5-diiodopentane, a catalytic amount of Aliquat ^R 336, and 60 mL of dioxane were added and stirred at reflux for 24 hours. HPLC analysis indicated that compound P was completely converted. After cooling, the mixture was diluted with 150 mL of methylene chloride and filtered over a diatomaceous bed. The filtrate was concentrated under reduced pressure to give Compound U. Performance Test Example 22 A 3% toluene solution of the stabilizer was prepared. The color of these solutions was measured in a 1 cm cell using a Byk-Gardner liquid color spectrometer. As can be seen in Table I, the tetralin triazine UV absorbers Compound E and Compound J have lower shades than the state of the art triazine UV absorber Tinuvin 1577.

[0308]

[Table 1]

Example 23 A thermogravimetric analysis was performed. Two samples were heated in air at 30-500 ° C., 10 ° C./min on a Perkin Elmer 7 series thermobalance. The purge gas flow rate was 2525 mL / min. Compound E was compared against the state of the art key stabilizers for polycarbonate. As seen in Table II, Compound E is significantly less volatile than the state of the art absorbent Tinuvin 1577. (T-10% and T-20% are the temperatures at which 10% and 20% weight loss occurs during the above heating protocol, respectively)

[0310]

[Table 2]

Example 24 A polycarbonate plaque was produced as follows. GE Lexan 105 Barefoot (
barefoot) 0.35% of natural flake polycarbonate resin (melt temperature 310-333 ℃)
Dry blended with stabilizer plus 0.10 wt% Mark ^R 2112 phosphite. Haak equipped with a 0.75 inch 25: 1 single mixing screw extruder
(Haake) Melted and mixed with a torque rheometer and extruded. Zone temperature 246, 265
, 295, and 304 ° C. Pull the extruded polycarbonate in a water bath,
Dried, pelletized and re-dried in a forced air oven at 120 ° C. for 4-48 hours. Using an Arburg "Allrounder" hydraulic extruder,
The pellets were injection molded at 340 ° C. and a residence time of 40 seconds to form plaques of 2 × 2.5 × 0.100 inches. The mold temperature was 100 ° C. An injection barrel temperature of 340 ° C was chosen to simulate extreme conditions. With the light source C, 2-observer, the reflection component was removed, and the yellow index and Delta E data were obtained using a Macbeth Color Eye colorimeter including the UV component. As can be seen in Table III, Compound E is more resistant to thermal yellowing than the state of the art absorbent Tinuvin 1577.

[0312]

[Table 3]

Example 25 A stabilized polycarbonate plaque was prepared as in Example 3, except that the injection molding temperature was lowered. The temperature is 305 ° C for the nozzle, 310 ° C for the nozzle side, 30 for the middle
The temperature was 0 ° C and the feed was 290 ° C. The plaques were oven-aged at 100 ° C. for 18 days. As can be seen in Table IV, compound E inhibits the thermal yellowing of the polycarbonate and has equal or better performance than state of the art tinuvin 1577 and UV-1164.

[0314]

[Table 4]

Example 26 A stabilized polycarbonate plaque was prepared as in Example 4. Plaques were exposed with a xenon arc weather O meter according to ASTM G-26 using test method B (Florida Miami conditions). Conditions were a dose of 0.35 W / m ^{2 at} 340 nm, alternating light and dark cycles, intermittent water spray, and a black panel temperature of 63 ° C. and 3 ° C. After 400 hours of exposure, Delta E (total color change) was measured. According to the results summarized in Table V,
Compound E is shown to be more effective than the state of the art stabilizers Tinuvin 1577 and Tinuvin 234 in reducing total color change.

[0316]

[Table 5]

Example 27 Stabilized coating composition A stabilized clear acrylic melamine composition was prepared, coated on a steel plate and subjected to an accelerated weather test as follows. Compound E (2% resin based on total solids), alone or Sanduvor ^R 3058HALS (0.67% or 1.0% in the resin total solids) in combination were dissolved in xylene, clear acrylic melamine formulation given in Table VI Was added. ED
Steel plates measuring 4 "la 12" precoated with 5050A E-coat, 764204 primer, and 542DF716 white base coat were obtained from ACT Laboratories (Laboratories, Inc, Hillside, Michigan). Draw-down method (Leneta Co.,
The panel was coated with the clearcoat formulation using WC-52 Wire-Cator ^™ from Ho-Ho-Kus, NJ. Dry the clearcoat at room temperature for 10 minutes,
Cured for 0 minutes.

[0318]

[Table 6]

Accelerated weathering according to ASTM G53 (GM cycle) for weathering under alternating cycles of (i) UV irradiation at 70 ° C. for 8 hours and (ii) condensation at 50 ° C. for 4 hours without UV irradiation. The test was performed by QUA. The specularity (gloss and image clarity, or DOI) is measured as a function of the weathering time. Compound E compared to unstabilized control
Alternatively, compositions containing both compound J have improved gloss and DOI retention. Compositions containing HALS S-3058 in addition to Compound E or Compound J also have improved gloss and DOI retention.

Although the present invention has been described with reference to certain preferred embodiments, workers skilled in the art will recognize that these modifications can be made without departing from the scope and spirit of the invention as defined by the appended claims. It is clear that variations are made.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 251/22 C07D 251/22 C C08K 5/3492 C08K 5/3492 (81) Designated countries EP (AT, BE) , CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA , GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY) , KG, KZ, MD, RU, TJ, TM), AL, AM, AU, AZ, BA, BB, BG, BR, BY, CA, CN, CU, CZ, EE, GD, E, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LV, MD, MG, MK, MN , MW, MX, NO, NZ, PL, RO, RU, SD, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Fischer, Robert G. 06430 Hue Field Syali Marain 41 F Term (Ref.) 4J002 AB01W AB02W AB04W AC00W AC01W AC03W AC08W AC09W AC12W AD01W AE00W BB00W BC03W BC05W BG01WBG03W BG00W BG00W BG00W BG00W BG00W BG00W BG00WBG03W BN15W CB00W CC03W CC16W CC18W CD00W CD19W CF00W CF01W CF05W CF06W CG00W CH00W CH02W CH05X CH06W CH07W CJ00W CK01W CK02W CL00W CM01W CM04W CN01W CN03W CP03W EU136 EU186 EV086 EV216 EV016 EDV 306306

Claims (20)

[Claims] 1. A compound of the formula (I) Wherein each A is independently nitrogen or methine optionally substituted by R ² , at least two A are nitrogen, and each of T and T ′ is independently a direct bond, carbon, oxygen, Nitrogen, sulfur, phosphorus, boron, silicon, or a functional group containing these elements; X is independently selected from hydrogen and a blocking group; and R ¹ and R ² are each independently a hydrocarbyl group, a functional hydrocarbyl group. Group, hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano; each of Y, R ³ and R ⁴ is independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, cyano, -O (hydrocarbyl) , -O (functional hydrocarbyl), -N (hydrocarbyl) (hydrocarbyl), -N (functional hydrocarbyl) (
Functional hydrocarbyl), - N (hydrocarbyl) (functional hydrocarbyl), - S (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (hydrocarbyl), - SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl) , -SO ₃ (functional hydrocarbyl), - COO (hydrocarbyl), - COO (functional hydrocarbyl), - CO (hydrocarbyl), - CO (functional hydrocarbyl, --OCO (hydrocarbyl), - OCO (functional hydrocarbyl) , -N (hydrocarbyl) (hydrocarbyl), - CONH _2, -CONH (hydrocarbyl), - CONH (functional hydrocarbyl), - CON (hydrocarbyl) (hydrocarbyl), - CON (hydrocarbyl) (functional hydrocarbyl), - CON (functional hydrocarbyl) (functional hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl) -COO (functional hydrocarbyl), - CO (functional Hidoroka Ruville), -OC
O (functional hydrocarbyl) or a hydrocarbyl group substituted by any of the above groups, wherein Z is Y, (Where L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or 1 to 24
X is independently selected from hydrogen and a blocking group; R ³ and R ⁴ are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), -O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl), - COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO (Functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano, and each G is independently a direct bond, nitrogen, sulfur , Oxygen, phosphorus, boron, silicon, selenium,
Tellurium, or a functional group containing these elements, each of m, n, and o is independently an integer between 0 and 4 (however, when both G are a direct bond, m, n And o are 2 and 10, and when one G is a direct bond, m
, N and o are between 1 and 9, and if no G is a direct bond, m, n
And o is between 0 and 8), p is an integer between O and 3, and q is an integer between O and 20). 2. The compound according to claim 1, wherein each G is a direct bond and m is 4, n, o, p and q are O. 3. The compound of formula (II) wherein T ′ is an oxygen atom, Y is a group L,
) The compound of claim 1, wherein L is Y, Z, R ³ and R ⁴ as defined above. 4. L is hydrogen; one or more hydroxy, alkoxy,
Carboxy, carboalkoxy, amino, amide, carbamate, or epoxy
Optionally substituted by one or more carbonyl groups, one or more carbonyl groups, acids
Alkyl of 1 to 24 carbon atoms which may contain an elementary or nitrogen atom in the chain;
One or more hydroxy, alkoxy, carboxy, carboalkoxy
Optionally substituted by amino, amide, carbamate, or epoxy groups
Is replaced by one or more carbonyl groups, oxygen or nitrogen atoms in the chain.
Alkenyl of 2 to 24 carbon atoms which may be included in one or more of hydroxy, alkoxy, chloro, cyano, carboxy
By carboxyloxy, amino, amide, carbamate, or epoxy group
Optionally substituted with one or more carbonyl groups, oxygen atoms, etc.
Or an aralkyl of 7 to 24 carbon atoms which may contain nitrogen atoms in the chain; formula XII -CH_Two-CH (OH) -CH_Two-0- (CH_Two-(CH_Two)_u-O-)_mm-D₁ (XII) (where D_lIs hydrogen and -CH_Two-CH (OH) -CH_Two-0H,Or R^{twenty five}A polyoxyalkylene group of the formula: XIII-CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-D_Two (XIII) (where D_TwoIs-(CH_Two) -CO-R^{twenty two}Or R^{twenty five}A polyoxyalkylene group of the formula VIII -YY-O-CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-D_Three (XIV) (where D_Three Is-(CH_Two) u-CO-R^{twenty two}Or R^{twenty five}A polyoxyalkylene group of the formula: XV- (CH_Two)_kk-CH (R^{twenty one}) -CO-B₁-(C_nnH_2nn-O-)_mm-C_nnH_2nn-B₁-D_Four (XV) (where D_FourIs hydrogen or R^{twenty five}A polyoxyalkylene group of the formula: XVI-CO-CH_Two-CH_Two-NH- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D_Five (XVI) (where D_FiveIs -NH_Two, -NH- (CH_Two)_Two-COO-R^{twenty three}Or -O-R^{twenty five}A polyoxyalkylene group of the formula: XVII-YY-O-CO-CH_Two-CH_Two-NH- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D_Five (XVII) (where D_FiveIs as defined under formula (XVI)); a polyoxyalkylene group of formula XVIII- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D₆ (XVIII) (where D₆Is -NH-CO-R^{twenty four}, -OR^{twenty five}, OH or H) a polyoxyalkylene group of formula XIX(Where D₇Is -OR^{twenty five}, -NHCOR^{twenty four}Or -OCH_TwoCH_TwoOR^{twenty five}R is selected from the group consisting of:^{twenty one}Is hydrogen or C₁-C₁₆ Alkyl and R^{twenty two}Is halogen or -O-R^{twenty three}And R^{twenty three}Is hydrogen, C₁-C₆Alkyl, C_Three-C₆Alkenyl, aryl, or aryl-C₁-C _Four -Alkyl, R^{twenty four}Is hydrogen, C₁-C₁₂Alkyl or aryl; R^{twenty five}Is C₁-C₁₆Alkyl, C_Five-C₁₂ Cycloalkyl, C_Three-C₆Alkenyl, C₁-C₁₂Al
Killaryl or aryl-C₁-C_FourAlkyl and R²⁶Is hydrogen or C₁-C_FourAlkyl and R²⁷Is hydrogen, C₁-C₁₈Alkyl, C_Three-C₆ Alkenyl, C₁-C₁₈ Alkoxy, halogen
Or aryl-C₁-C_Four-Alkyl, R²⁸And R²⁹Is independently hydrogen, C₁-C₁₈ Alkyl, C_Three-C₆Alkenyl, C₁-C₁₈ Alkoxy or halogen; R³⁰Is hydrogen, C₁-C_FourAlkyl or CN, YY is unsubstituted or substituted C_Two-C₂₀ Alkyl, Kk is zero or an integer from 1-16, and B_lIs 0 or NH; Mm is an integer from 2 to 60; Nn is an integer from 2 to 6; and U is an integer from 1 to 4. (5) TZ is Wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms, X is independently selected from hydrogen and a block group, R ³ and R ⁴ is independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), - O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl) , -COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO The compound according to claim 3, which is (functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano. 6. All G are direct bonds, m is 4, nq is 0, and all A are nitrogen, and the compound is of the formula Wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms, X is independently selected from hydrogen and a block group, R ³ and R ⁴ is independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), - O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl) , -COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO 6. A compound according to claim 5, which is (functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano. 7. T is a direct bond and Z is Wherein the compound is of the formula: Wherein A, G, T ′, X, Y, R ¹ to R ⁴ and the subscripts m, n, o, p, and q are defined as in claim 1. Item 7. The compound according to Item 1. 8. All G are direct bonds, m = 4, n, o, p, and q are 0, all A are nitrogen, and the compound is of the formula Wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms, X is independently selected from hydrogen and a block group, R ³ and R ⁴ is independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), - O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl) , -COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO The compound of claim 7, which is (functional hydrocarbyl), —CO (functional hydrocarbyl), —OCO (functional hydrocarbyl), —N (functional hydrocarbyl) (functional hydrocarbyl) or cyano. 9. A compound of the formula (VII) (Where A, T, T ′, R ¹ , R ² , Y, Z, R ³ , R ⁴ , G, m, n, o, p, q are defined as in claim 1, and r is 2 or 3, when r is 2, X 'is ^{-CO-R 16 -CO -, -} CO 2 -R 16 -CO 2 -, - SO 2 -R 16 -SO 2 -, - CO-N
HR ¹⁷ -NH-CO-, -CO- (CH ₂ ) _u -O- (CH _2- (CH ₂ ) _u -O-) _mm- (CH ₂ ) _u -CO-, a polyoxyalkylene bridge member, or Embedded image And when r is 3, X ′ is-(-CO ₂ -R ¹⁶ ) R ¹⁹ ,-(-CONH-R ¹⁶ ) R ¹⁹ ,-(-SO ₂ -R ¹⁶ ) R ¹⁹ R ¹⁶ is C ₂ -C ₁₀ alkylene, C ₂ -C ₁₀ oxoalkylene or C ₂ -C ₁₀ dithioalkylene, phenylene, naphthylene, diphenylene, or C ₂ -C ₆ alkenylene, and R ¹⁷ is C _2- C ₁₀ alkylene, phenylene, naphthylene, methylene diphenylene or C ₇ -C ₁₅ alkyl phenylene, and R ¹⁸ is C ₂ -C ₁₀ alkylene or C ₄ -C ₂₀ interrupted by one or more oxygen atoms. R ¹⁹ is C ₃ -C ₁₀ alkanthryl and R ²⁰ is C ₄ -C ₁₀ alkantetrile. 10. A compound of the formula (VI) Wherein A, T, X, Z, R ¹ , R ² , R ³ , R ⁴ , G, m, n, o, p, q are defined as in claim 1 and r is 2 and 4 And when r is 2, D represents C ₂ -C ₁₆ alkyl, C ₄ -C ₁₂ alkenyl, xylylene, C _3- interrupted by one or more oxygen atoms. C ₂₀ alkyl, hydroxy-substituted C ₃ -C ₂₀ alkyl interrupted by one or more oxygen atoms, -CH ₂ CH (OH) CH ₂ OR ¹⁵ -OCH ₂ CH (OH) C
H ₂ , -CO-R ¹⁶ CO-, -CO-NH-R ¹⁷ -NH-CO-,-(CH ₂ ) _s -COO-R ¹⁸ -OCO- (CH ₂ ) _s , formula XX -CH _{2- CH (OH) -CH 2 -O- (} CH 2 - (CH 2) u -O-) mm -CH 2 -CH (OH) -CH 2 - polyoxyalkylene bridge member of (XX), formula XXI -CO _{- (CH 2) u -O- (} CH 2 - (CH 2) u -O-) mm - (CH 2) a polyoxyalkylene bridge member of _u -CO- (XXl), wherein XXII -YY-O-CO _{(CH 2) u -O- (CH} 2 - (CH 2) u -O-) mm - (CH 2) u -COO-YY- a polyoxyalkylene bridge member of (XXII), formula XXIII - (CH _{2) ^{kk -CH (R 21) -CO-}} B 1 - (C nn -H 2nn -O-) mm -C nn H 2nn -B 1 -CO-CH (R 21) - (CH 2) kk - (XXIll) A polyoxyalkylene bridging member of the formula XXIV: A member of the formula XXV -YY-O-CO- (CH ₂ ) ₂ -NH- (C _nn H _2nn -O-) _mm -C _nn H _2nn -NH- (CH ₂ ) ₂ COO-YY _-A polyoxyalkylene bridge member of (XXV), a formula _XXVI- (C _nn H _2nn -O-) _mm -C _nn H _2nn -a polyoxyalkylene bridge member of (XXVI), and a formula XXVII -CH (CH ₃ )- CH _2- (O-CH (CH ₃ ) -CH ₂ ) _a- (O-CH ₂ -CH ₂ ) _b- (O-CH ₂ -CH (CH ₃ ) _c- (XXVII) (where a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0
R ²¹ is hydrogen or C ₁ -C ₁₆ alkyl, R ²² is halogen or —OR ²³ , R ²³ is hydrogen, C ₁ -C ₆ alkyl, C _3- C ₆ alkenyl, aryl, or aryl-C _1-
C ₄ - alkyl, R ²⁴ is hydrogen, C ₁ -C ₁₂ alkyl or aryl, R ²⁵ is C _l -C ₁₆ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₂ alkyl or aryl -C _l ^- is a C ₄ alkyl, R ²⁶ is hydrogen or C _l -C ₄ alkyl, R ²⁷ is hydrogen, C ₁ - C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₈ alkoxy, halogen or aryl-C ₁ -C ₄ alkyl, wherein R ²⁸ and R ²⁹ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, or
C ₁ -C ₁₈ alkoxy, or halogen, R ³⁰ is hydrogen, C ₁ -C ₄ alkyl or CN, YY is unsubstituted or substituted C ₂ -C ₂₀ alkyl, kk is zero or 1-16 Where B _l is O or NH, mm is an integer from 2 to 60, nn is an integer from 2 to 6, u is an integer from 1 to 4, and r is 3. In, D is If r is 4, D is Wherein R ¹⁹ is C ₃ -C _{10 alkantotril} , R ²⁰ is C ₄ -C _{10 alkantetrile} ,
s is 1-6), and R ¹⁵ is C ₂ -C ₁₀ alkyl, C ₂ -C ₁₀ oxoalkyl or C ₂ -C ₁₀ dithioalkyl,
Phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl or phenylene -XX- phenylene (wherein,,, XX is _{-O-, -S-, -SO 2 -,} - CH 2 - or -C (CH _{3) And} R ¹⁶ is C ₂ -C ₁₀ alkyl, C ₂ -C ₁₀ oxoalkyl or C ₂ -C ₁₀ dithioalkyl, phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl, provided that r If is 3, alkenyl has at least 3 carbons) and R ¹⁷ is C ₂ -C ₁₀ alkyl, phenyl, naphthyl, diphenyl, or C ₂ -C ₆ alkenyl, methylene diphenylene, or C ₄ -C ₁₅ alkylphenyl and R ¹⁸ is C ₂ -C ₁₀ alkyl or C ₄ -C ₂₀ alkyl interrupted by one or more oxygen atoms. 11. A compound of the formula (IX)(Where A, T, T ', X, Y, R¹, R^Two, R^Three, R^Four, G, m, n, o, p, and q are defined in claim 1
Where r is an integer between 2 and 4, and if r is 2, D is C_Two-C₁₆ Alkylene, C_Four-C₁₂ Alkenylene, xylylene
Len, C interrupted by one or more oxygen atoms_Three-C₂₀Alkylene, one
Hydroxy-substituted C interrupted by one or more oxygen atoms_Three-C₂₀Archire
, -OOCR¹⁴COO-, -CH_TwoCH (OH) CH_TwoO-R¹⁵-OCH_TwoCH (OH) CH_Two, -CO-R¹⁶-CO-, -CO-NH-R ¹⁷ -NH-CO-, and-(CH_Two)_s-COO-R¹⁸-OCO- (CH_Two)-, And when r is 3, D isWhen r is 4, D is(Where R¹⁹Is C_Three-C_l0Alcantril, R²⁰Is C_Four-C_l0Alkantetrile,
s is 1-6), r is an integer between 2 and 4, and if r is 2, D is C_Two-C₁₆ Alkylene, C_Four-C₁₂ Alkenylene, xylylene, one or more
C interrupted by an oxygen atom of_Three-C₂₀Alkylene, one or more oxygen sources
Hydroxy-substituted C interrupted by child_Three-C₂₀Alkylene, -CH_TwoCH (OH) CH_Two0-R¹⁵-OCH _Two CH (OH) CH_Two, -CO-R¹⁶-CO-, -CO-NH-R¹⁷-NH-CO-, and-(CH_Two)_s-COO-R¹⁸-0CO- (CH_Two )_s When r is 3, D is selected from the group consisting ofWhen r is 4, D is(Where R¹⁹Is C_Three-C_l0Alcantril, R²⁰Is C_Four-C_l0Alkantetrile,
s is 1-6) and R⁸Is C_l-C₁₈ Alkyl, C_Three-C₁₈Interrupted by alkenyl, O, N or S, and
And / or C substituted by OH_Three-C₂₀Alkyl, -P (O) (OR¹⁴)_Two, -N (R⁹) (R^l0),
Or -OCOR^1lAnd / or C substituted by OH₁-C_Four Is an alkyl
Or glycidyl, cyclohexyl or C₇-C₁₁Phenylalkyl; R⁹And R^TenAre each independently of the other_l-C_l2Alkyl, C_Three-C₁₂Alkoxyalkyl, C _Four -C₁₆Dialkylaminoalkyl or C_Five-C₁₂Cycloalkyl, or together
Then, R⁹And R^l0Is C_Three-C₉ Alkylene, C_Three-C₉Oxaalkylene or C_Three-C₉A
Zalkylene and R^l1Is C_l-C₁₈Alkyl, C_Two-C₁₈Alkenyl or phenyl; R¹²Is C_l-C₁₈Alkyl, C_Two-C₁₈ Alkenyl, phenyl, C_l-C₁₂Alkoxy, Fe
Noxy, C_l-C₁₂Alkylamino, phenylamino, tolylamino or naphthyl
Amino and R¹³Is Cl^-C₁₂Alkyl, phenyl, naphthyl or C₇-C₁₄Alkylphenyl
R¹⁴Is C₁-C₁₂Alkyl or phenyl; R¹⁵Is C_Two-C_l0Alkylene, phenylene or phenylene-X-phenylene group (wherein
X is -O-, -S-, -SO_Two-, -CH_Two-Or-C (CH_Three)_Two-Is) and R¹⁶Is C_Two-C_l0Alkylene, C_Two-C_l0Oxoalkylene or C_Two-C_l0Dithioalkyle
, Phenylene, naphthylene, diphenylene or C_Two-C₆ Alkenylene,
R¹⁷Is C_Two-C_TenAlkylene, phenylene, naphthylene, methylenediphenylene or
Is C₇-C₁₅ Alkylphenylene and R¹⁸Is C_Two-C_TenInterrupted by alkylene or one or more oxygen atoms
C_Four-C₂₀ A compound which is alkylene). 12. T is a direct bond and Z is of the general formula III Wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbyl group of 1 to 24 carbon atoms, X is independently selected from hydrogen and a block group, R ³ and R ⁴ is independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl), - O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl) , -COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO 10. The substituent according to claim 9, which is a substituent of (functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano. Compound. 13. T is a direct bond and Z is of the general formula III Wherein R ¹ , R ² , G, m, n, o, p, and q are defined as in claim 10, wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or 1 to Is a functional hydrocarbyl group of 24 carbon atoms, X is independently selected from hydrogen and a blocking group, and R ³ and R ⁴ are independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, -O (hydrocarbyl) , -O (functional hydrocarbyl), - S (hydrocarbyl), -SO ₂ (hydrocarbyl), - SO ₃ (hydrocarbyl), - COO (hydrocarbyl)
, -CO (hydrocarbyl), --OCO (hydrocarbyl), - N (hydrocarbyl) (hydrocarbyl), - S (functional hydrocarbyl), - SO ₂ (functional hydrocarbyl), - SO ₃ (functional hydrocarbyl), - COO 11. The substituent of claim 10, which is a substituent of (functional hydrocarbyl), -CO (functional hydrocarbyl), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional hydrocarbyl) or cyano. Compound. 14. L is hydrogen; one or more hydroxyl, carboxyl, carboalkoxy, amino
Substituted by an amino, epoxy or amino group, and one or more
Contains further carbonyl, oxygen or nitrogen atoms in the chain, as the case may be.
Alkyl, hydroxyl, carboxyl, epoxy, or amino groups of 1 to 24 carbon atoms,
Substituted and has one or more carbonyl groups, oxygen or nitrogen atoms
An alkenyl of 2 to 24 carbon atoms, optionally containing in the chain; optionally substituted by a hydroxyl, carboxyl, or amino group;
And 5 to 24 optionally containing a carbonyl group, oxygen or nitrogen atom in the ring
Cycloalkyl of carbon atoms; and optionally substituted by hydroxyl, carboxyl or amino groups,
From 7 to 24 carbonyl groups, oxygen and / or nitrogen atoms in the ring
Aralkyl of a carbon atom of the formula XII -CH_Two-CH (OH) -CH_Two-0- (CH_Two-(CH_Two)_u-O-)_mm-D₁ (XII) (where D_lIs hydrogen and -CH_Two-CH (OH) -CH_Two-OH,Or R^{twenty five}A polyoxyalkylene group of the formula: XIII-CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-D_Two (XIII) (where D_TwoIs-(CH_Two) -CO-R^{twenty two}Or R^{twenty five}A polyoxyalkylene group of the formula VIII -YY-O-CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-D_Three (XIV) (where D_Three Is-(CH_Two)_u-CO-R^{twenty two}Or R^{twenty five}A polyoxyalkylene group of the formula: XV- (CH_Two)_kk-CH (R^{twenty one}) -CO-B₁-(C_nnH_2nn-O-)_mm-C_nnH_2nn-B₁-D_Four (XV) (where D_FourIs hydrogen or R^{twenty five}A polyoxyalkylene group of the formula: XVI-CO-CH-CH-NH- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D_Five (XVI) (where D_FiveIs -NH_Two, -NH- (CH_Two)_Two-COO-R^{twenty three}Or -O-R^{twenty five}A polyoxyalkylene group of the formula: XVII-YY-O-CO-CH_Two-CH_Two -NH- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D_Five (XVII) (where D_FiveIs as defined under formula (XVI)); a polyoxyalkylene group of formula XVIII- (C_nnH_2nn-O-)_mm-C_nnH_2nn-D₆ (XVIII) (where D₆Is -NH-CO-R^{twenty four}, -OR^{twenty five}, OH or H) a polyoxyalkylene group of the formula XIX(Where D₇Is -OR^{twenty five}, -NHCOR^{twenty four}Or -OCH_TwoCH_TwoOR^{twenty five}A) a polyoxyalkylene group of formula XX -CH_Two-CH (OH) -CH_Two-O- (CH_Two-(CH_Two)_u-O-)_mm-CH_Two-CH (OH) -CH_Two-A polyoxyalkylene bridging member of (XX), of the formula: XXI -CO- (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-(CH_Two)_u-CO- (XXl), a polyoxyalkylene bridging member of the formula: XXII -YY-O-CO (CH_Two)_u-O- (CH_Two-(CH_Two)_u-O-)_mm-(CH_Two)_u-COO-YY- (XXII), a polyoxyalkylene bridging member of the formula: XXIII-(CH_Two)_kk-CH (R^{twenty one}) -CO-B_1-(C_nn-H_2nn-O-)_mm-C_nnH_2nn-B₁-CO-CH (R^{twenty one})-(CH_Two)_kk-(XXIll), a polyoxyalkylene bridging member of the formula: XXIVA polyoxyalkylene bridging member of the formula XXV-YY-O-CO- (CH_Two)_Two-NH- (C_nnH_2nn-O-)_mm-C_nnH_2nn-NH- (CH_Two)_TwoCOO-YY- (XXV), a polyoxyalkylene bridging member of the formula: XXVI- (C_nnH_2nn-O-)_mm-C_nnH_2nn-(XXVI), a polyoxyalkylene bridging member of the formula: XXVII -CH (CH_Three) -CH_Two-(O-CH (CH_Three) -CH_Two)_a-(O-CH_Two-CH_Two)_b-(O-CH_Two-CH (CH_Three)_c-(XXVII), wherein a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0, selected from the group consisting of:^{twenty one}Is hydrogen or C₁-C₁₆ Alkyl and R^{twenty two}Is halogen or -O-R^{twenty three}And R^{twenty three}Is hydrogen, C₁-C₆Alkyl, C_Three-C₆Alkenyl, aryl, or aryl-C₁-C _Four -Alkyl, R^{twenty four}Is hydrogen, C₁-C₁₂Alkyl or aryl; R^{twenty five}Is C₁-C₁₆Alkyl, C_Five-C₁₂ Cycloalkyl, C_Three-C₆Alkenyl, C₁-C₁₂Al
Killaryl or aryl-C_l-C_FourAlkyl and R²⁶Is hydrogen or C_l-C_FourAlkyl and R²⁷Is hydrogen, C_l-C₁₈Alkyl, C_Three-C₆ Alkenyl, C_l-C₁₈ Alkoxy, halogen
Or aryl-C_l-C_Four-Alkyl, R²⁸And R²⁹Is independently hydrogen, C_l-C₁₈ Alkyl, C_Three-C₆Alkenyl, C_l-C₁₈ Alkoxy or halogen; R³⁰Is hydrogen, C_l-C_FourAlkylOr CN, YY is unsubstituted or substituted C_Two-C₂₀13. An alkylene, kk is zero or an integer from 1-16, mm is an integer from 2 to 60, nn is an integer from 2 to 6, and u is an integer from 1 to 4. Compound. 15. L is hydrogen; optionally substituted by one or more hydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups, and one or more carbonyl groups, oxygen atoms or nitrogen atoms An alkyl of 1 to 24 carbon atoms, optionally containing in the chain; optionally substituted by a hydroxyl, carboxyl, epoxy or amino group, and one or more carbonyl groups, oxygen or nitrogen atoms in the chain An alkenyl of 2 to 24 carbon atoms, optionally containing; optionally substituted by a hydroxyl, carboxyl, or amino group;
And a cycloalkyl of 5 to 24 carbon atoms optionally containing a carbonyl group, oxygen or nitrogen in the ring; optionally substituted by a hydroxy, carboxyl or amino group and containing a carbonyl, oxygen or nitrogen in the ring Aralkyl of 7 to 24 carbon atoms which may be of the formula XII -CH ₂ -CH (OH) -CH ₂ -O- (CH _2- (CH ₂ ) _u -O-) mm-D ₁ (XII) among, D _l is _{hydrogen, -CH 2 -CH (OH) -CH} 2 -0H, embedded image Or a R ²⁵ ) polyoxyalkylene group of the formula: XIII-CO- (CH ₂ ) _u -O- (CH _2- (CH ₂ ) _u -O-) _mm -D ₂ (XIII) ₂ is — (CH ₂ ) —CO—R ²² or R ²⁵ ); a polyoxyalkylene group of the formula VIII—YY—O—CO— (CH ₂ ) _u —O— (CH ₂ — (CH ₂ ) _u -O-) _mm -D ₃ (XIV) wherein D ₃ is-(CH ₂ ) _u -CO-R ²² or R ²⁵ ; a formula XV-(CH ₂ ) _kk- CH (R ²¹ ) -CO-B _1- (C _nn H _2nn -O-) _mm -C _nn H _2nn -B ₁ -D ₄ (XV) wherein D ⁴ is hydrogen or R ²⁵ polyoxyalkylene group; formula XVI -CO-CH-CH-NH- (C nn H 2nn -O-) mm -C nn H 2nn -D 5 (XVI) ( wherein, D ₅ is -NH ₂ -NH- (CH ₂ ) ₂ —COO—R ²³ or —OR ²⁵ ); a polyoxyalkylene group of the formula: XVII—YY—O—CO—CH ₂ —CH ₂ —NH— (C _nn H _2nn —O—) _mm A polyoxyalkylene group of -C _nn H _2nn -D ₅ (XVII), wherein D ₅ is as defined under formula (XVI); formula _XVIII- (C _nn H _2nn -O-) _{mm -C nn H 2nn -D 6 (} XVIII) ( Among, D ₆ is -NH-CO-R ^24, a polyoxyalkylene group which is -OR ^25, OH or H); formula XIX embedded image Wherein D ₇ is —OR ²⁵ , —NHCOR ²⁴ or —OCH ₂ CH ₂ OR ²⁵ ; a polyoxyalkylene group of the formula XX —CH ₂ —CH (OH) —CH ₂ —O— (CH ₂ -(CH ₂ ) _u -O-) _mm -CH ₂ -CH (OH) -CH _2- (XX), a polyoxyalkylene bridging member of the formula: XXI -CO- (CH ₂ ) _u -O- (CH _{2 - (CH 2) u -O-)} mm - (CH 2) u -CO- (XXl), polyoxyalkylene bridge member of; formula XXII -YY-O-CO (CH 2) u -O- (CH 2 _{- (CH 2) u -O-)} mm - (CH 2) u -COO-YY- (XXII), a polyoxyalkylene bridge member; formula _{XXIII - (CH 2) kk -CH} (R 21) CO-B _{1 - (C nn -H 2nn -O-} ) mm -C nn H 2nn -B 1 -CO-CH (R 21) - (CH 2) kk - (XXIll), polyoxyalkylene bridge member of; formula XXIV [ Formula 30 A polyoxyalkylene bridging member of the formula XXV -YY-O-CO- (CH ₂ ) ₂ -NH- (C _nn H _2nn -O-) _mm -C _nn H _2nn -NH- (CH ₂ ) ₂ COO-YY - (XXV), a polyoxyalkylene bridge member of; formula _{XXVI - (C nn H 2nn -O-} ) mm -C nn H 2nn - (XXVI), polyoxyalkylene bridge members; formula XXVII -CH (CH ₃₎ -CH _2- (O-CH (CH ₃ ) -CH ₂ ) _a- (O-CH ₂ -CH ₂ ) _b- (O-CH ₂ -CH (CH ₃ ) _c- (XXVII) a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0
R ²¹ is hydrogen or C ₁ -C ₁₆ alkyl, R ²² is halogen or —OR ²³ , R ²³ is hydrogen, C _1- C ₆ alkyl, C ₃ -C ₆ alkenyl, aryl, or aryl-C _1-
C ₄ - alkyl, R ²⁴ is hydrogen, C ₁ -C ₁₂ alkyl or aryl, R ²⁵ is C ₁ -C ₁₆ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₂ alkylaryl or aryl-C ₁ -C ₄ alkyl, R ²⁶ is hydrogen or C ₁ -C ₄ alkyl, R ²⁷ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₁ -C ₁₈ alkoxy, halogen or aryl-C ₁ -C ₄ -alkyl, wherein R ²⁸ and R ²⁹ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C _1- C ₁₈ alkoxy or halogen, R ³⁰ is hydrogen, C ₁ -C ₄ alkyl or CN, YY is unsubstituted or substituted C ₂ -C ₂₀ alkylene, kk is zero or an integer of 1-16. 14. The compound of claim 13, wherein mm is an integer from 2 to 60, nn is an integer from 2 to 6, and u is an integer from 1 to 4. 16. A compound of the formula (VIII) (Wherein, A, T, T ', X, Y, Z, R 1, R 2, R 3, G, m, n, o, p, and q are defined as in claim 1, R ⁴ Are linear alkylene of 1 to 12 carbon atoms, branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene substituted by cyclohexyl, alkylene interrupted by cyclohexyl alkylene substituted by phenylene, alkylene interrupted by phenylene, benzylidene, -S -, - SS-, -SES- , -SO -, - SO 2 -, - SO-E-SO -, - SO 2 - E-SO _2- , -CH ₂ -NH-E-NH-CH ₂ -and (Wherein E is alkyl of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, 8 to 12 alkylenes interrupted by cyclohexylene, terminal of 8 to 12 of cyclohexylene 12 is an alkylene of 2 carbon atoms, wherein r is an integer between 2 and 4. 17. All G are direct bonds and m = 4, n, o, p, and q are zero.
Wherein all A are nitrogen and the compound is of the formula(Wherein X is independently selected from hydrogen and a blocking group; L, R^ThreeAnd R^FourIs independently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen
, Hydroxyl, -O (hydrocarbyl), -O (functional hydrocarbyl), -S (hydrocarbyl)
Calville), -SO_Two(Hydrocarbyl), -SO_Three(Hydrocarbyl), -COO (hydrocarbyl)
Building), -CO (hydrocarbyl), -OCO (hydrocarbyl), -N (hydrocarbyl)
Drocarbyl), -S (functional hydrocarbyl), -SO_Two(Functional hydrocarbyl), -SO _Three (Functional hydrocarbyl), -COO (functional hydrocarbyl), -CO (functional hydrocarbyl)
Rubil), -OCO (functional hydrocarbyl), -N (functional hydrocarbyl) (functional
Or carboxy) or cyano). 18. The formula (XXXV) Wherein A, R ¹ , R ² , G, m, n, o, p, q are defined as in claim 1 and each Hal is bromine, chlorine, or iodine. 19. A compound of the formula (XXXVI) Wherein A, R ¹ , R ² , G, m, n, o, p, q are defined as in claim 1 and each Hal is bromine, chlorine, or iodine. 20. Inclusion of an actinic radiation stabilizing composition in said material in an amount effective to stabilize the material against the effects of actinic radiation, thereby stabilizing the material subject to actinic radiation degradation. How to