JP4126364B2 - Benzotriazole UV absorber with enhanced durability - Google Patents

Benzotriazole UV absorber with enhanced durability Download PDF

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JP4126364B2
JP4126364B2 JP32209797A JP32209797A JP4126364B2 JP 4126364 B2 JP4126364 B2 JP 4126364B2 JP 32209797 A JP32209797 A JP 32209797A JP 32209797 A JP32209797 A JP 32209797A JP 4126364 B2 JP4126364 B2 JP 4126364B2
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JPH10140089A (en
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ディビッド デベリス アンソニイ
ヴォルフ ジャン−ピエール
スハドルニク ジョセフ
ゲール ウッド マービン
ラビチャンドラン ラマナサン
イエンガー レバシ
エドワード デトレフセン ロバート
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チバ ホールディング インコーポレーテッドCiba Holding Inc.
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472Five-membered rings
    • C08K5/3475Five-membered rings condensed with carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D249/00Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18Benzotriazoles
    • C07D249/20Benzotriazoles with aryl radicals directly attached in position 2
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518Five-membered rings
    • C07F9/65188Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/48Stabilisers against degradation by oxygen, light or heat

Description

[0001]
BACKGROUND OF THE INVENTION
Benzotriazole-based UV absorbers in which the benzene ring is replaced by an electron withdrawing part exhibit enhanced durability and a low loss rate when blended into an automobile coating.
[0002]
[Prior art and problems to be solved by the invention]
Benzotriazoles have long been an important part of UV absorbers and are accepted as commercially important for many industrial applications. The prior art is numerous for their production and use. However, the demands are always more stringent, and demand and research continue to be on a more stable and durable benzotriazole. Due to environmental concerns and the shift of HAPS solvents to non-HAPS solvents such as esters, ethers or ketones, HAPS solvents such as xylene are gradually surfaced and enhanced durability for automotive coatings Demand is even more urgent. In fact, as seen in the publication “J.L. Gerioc et al., Proc. 36th Annual Tech. Sym. (Cleaveland Coating Society), May 18, 1993”, the automotive industry is from automotive paints and coatings. Most interested in UVA loss.
[0003]
Vyscomol Soedin, Ser. A,18(3), 553 (1976) describes that the hydrogen bond strength and light stability in benzotriazoles are in a linear relationship.
[0004]
J. et al. E. Pickett et al. , Angew. Makromol. Chem. 232, 229 (1995) describes the photodegradation of benzotriazole-based UV absorber absorbers in poly (methyl methacrylate) films. Regardless of whether the substitution disrupts intermolecular hydrogen bonds, which are important for stability, structural changes generally only cause slight differences in degradation rates. Pickett et al. Did not test any benzotriazole containing both electron withdrawing and electron donating groups as in the present invention.
[0005]
The prior art leads to the conclusion that strengthening hydrogen bonding makes benzotriazoles more stable, but does not teach how to do this. Although the present invention discloses benzotriazoles that exhibit this enhanced durability, surprisingly, this enhanced durability is not always related to greater hydrogen bond strength. In fact, compounds with enhanced durability often have weaker, less strong hydrogen bonds.
[0006]
U.S. Pat. 4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5, 607,987 describe selected benzotriazoles in which the 3-position of the hydroxyphenyl ring is substituted with an α-cumyl group, which show very good stability in automotive coatings. These benzotriazoles represent the current state of the art. The present invention is directed to producing benzotriazoles that exhibit even greater durability and lower loss rates than prior art benzotriazoles.
[0007]
U.S. Pat. 5,278,314; 5,280,124; 5,436,349 and 5,516,914 describe red-shifted benzotriazoles. In these benzotriazoles, the 5-position of the benzo ring is substituted with a thioether, alkylsulfonyl or phenylsulfonyl moiety. Red shifting of benzotriazoles is desirable for spectral reasons. The group at the 5-position, which is also electron withdrawing, provides additional advantages in terms of the low loss rate and durability found in the present invention.
[0008]
[Means for Solving the Problems]
The present invention relates to benzotriazoles having enhanced durability and low loss rate when formulated in automotive coatings.
[0009]
More particularly, the present invention is a coating composition stabilized with benzotriazole, wherein the coating composition exhibits enhanced durability and low loss rate when the benzotriazole is incorporated into the composition. And
(A) From the group consisting of thermosetting acrylic melamine resin, acrylic urethane resin, epoxy carboxy resin, silane-modified acrylic melamine, acrylic resin having carbamate side groups cross-linked with melamine, or acrylic polyol resin cross-linked with melamine containing carbamate groups Selected resin, and
(B) 0.01 to 5% by weight of formula A, B, C or D based on resin solids
Embedded image
{Where
G1, G2Or T represents an electron withdrawing group;
G1Represents a hydrogen atom or a halogen atom;
G2Is a halogen atom, nitro group, cyano group, RThreeSO-, RThreeSO2-, -COOGThree, CFThree-, -P (O) (C6HFive)2, -CO-GThree, -CO-NH-GThree, -CO-N (GThree)2, -N (GThree) -CO-GThree,
Embedded image
Represents;
GThreeIs a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, carbon A phenylalkyl group having 7 to 15 atoms, a phenyl group, the phenyl group substituted with 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring;
R1Is a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, carbon A phenylalkyl group having 7 to 15 atoms, a phenyl group, the phenyl group substituted with 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring;
R2Is a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, carbon Represents a phenylalkyl group having 7 to 15 atoms, a phenyl group, the phenyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the phenylalkyl group,
Or R2Is a hydroxyl group or -ORFour(Wherein RFourRepresents a linear or branched alkyl group having 1 to 24 carbon atoms. ); One or more -OH, -OCO-R11, -ORFour, -NCO or -NH2Or the above alkyl group substituted by a mixture thereof; or one or more —O—, —NH— or —NRFour-Interrupted by groups or mixtures thereof and unsubstituted or one or more -OH, -ORFourOr -NH2Represents the above alkyl group or the above alkenyl group optionally substituted by a group or a mixture thereof;
Or R2Is -SRThree, -NHRThreeOr -N (RThree)2 Or
Or R2Is-(CH2)m-CO-X- (Z)p-YR15
[Wherein X represents —O— or —N (R16)-
Y is —O— or —N (R17)-
Z represents an alkylene group having 2 to 12 carbon atoms, 1 to 3 nitrogen atoms, an oxygen atom, or an alkylene group having 4 to 12 carbon atoms interrupted by a mixture thereof, or 3 to 12 carbon atoms. An alkylene group, butenylene group, butynylene group, cyclohexylene group or phenylene group, each of which is substituted with a hydroxyl group,
m represents 0, 1 or 2;
p represents 1 or each of X and Y is —N (R16)-And -N (R17) Also represents 0,
R15Is a group —CO—C (R18) = C (H) R19Or Y is -N (R17)-Represents R17Together with the group -CO-CH = CH-CO-
R18Represents a hydrogen atom or a methyl group,
And R19Is a hydrogen atom, a methyl group or —CO—X—R20Represents
R20Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a formula
Embedded image
(In the formula, symbol G1, G2, R1, X, Z, m and p have the above definitions. )
And R16And R17Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 12 carbon atoms interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or 7 carbon atoms. Represents 15 to 15 aralkyl groups,
And R when Z represents an ethylene group.16Is R17Together with it forms an ethylene group. ];
n represents 1 or 2,
When n represents 1, RFiveIs Cl, OR6Or NR7R8Or
RFiveIs -PO (OR12)2, -OSi (R11)ThreeOr -OCO-R11Or -O-, -S- or -NR11Interrupted by-and unsubstituted or -OH or -OCO-R11A linear or branched alkyl group having 1 to 24 carbon atoms, which may be substituted by: an unsubstituted or cycloalkyl group having 5 to 12 carbon atoms substituted by —OH; A straight-chain or branched alkenyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, substituted with —OH, —CH2-CHOH-R13Or represents a glycidyl group;
R6Is a hydrogen atom, unsubstituted or one or more OH, ORFourOr NH2Represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms substituted by a group, or -OR6Is-(OCH2CH2)wOH or-(OCH2CH2)wORtwenty oneIn which w represents 1 to 12 and Rtwenty oneRepresents an alkyl group having 1 to 12 carbon atoms);
R7And R8Independently of one another, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; —O—, —S— or —NR11A straight or branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aryl group having 1 to 3 carbon atoms interrupted by- Represents a hydroxyalkyl group, or
R7And R8Represents, together with the N atom, a pyrrolidine ring, piperidine ring, piperazine ring or morpholine ring;
When n represents 2, RFiveIs a divalent group -O-R9-O- or -N (R11-RTen-N (R11)-Represents one of;
R9Is an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, an alkynylene group having 4 carbon atoms, a cyclohexylene group, —O— or —CH.2-CHOH-CH2-O-R14-O-CH2-CHOH-CH2Represents a linear or branched alkylene group of 4 to 10 carbon atoms interrupted by-
RTenIs a linear or branched alkylene group having 2 to 12 carbon atoms which may be interrupted by -O-, cyclohexylene group or
Embedded image
Or
Or RTenAnd R11Together with two nitrogen atoms forms a piperazine ring,
R14Is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 4 to 10 carbon atoms interrupted by —O—, a cycloalkylene group, an arylene group, or
Embedded image
Represents
R7And R8Each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, or R represents7And R8Together represent an alkylene group having 4 to 6 carbon atoms, a 3-oxapentamethylene group, a 3-iminopentamethylene group or a 3-methyliminopentamethylene;
R11Is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a straight chain or branched chain alkenyl group having 3 to 8 carbon atoms, carbon Represents an aryl group having 6 to 14 atoms or an aralkyl group having 7 to 15 carbon atoms;
R12Is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group of 16 to 16 or an aralkyl group of 7 to 15 carbon atoms;
R13Is H, -PO (OR12)2A straight-chain or branched alkyl group having 1 to 18 carbon atoms, an unsubstituted or substituted phenyl group with OH, an aralkyl group having 7 to 15 carbon atoms, or —CH2OR12Represents;
RThreeIs an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a 7 to 15 carbon atom. A phenylalkyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group or perfluoroalkyl moiety substituted by one or two alkyl groups having 1 to 4 carbon atoms, having 6 to 16 carbon atoms; Represents a certain 1,1,2,2-tetrahydroperfluoroalkyl group;
L represents an alkylene group having 1 to 12 carbon atoms, an alkylidene group having 2 to 12 carbon atoms, a benzylidene group, a p-xylylene group or a cycloalkylidene group, and
T is -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO-, -CO-NGThree-E-NGThree-CO- or -NGThree-CO-E-CO-NGThree-(Wherein E is interrupted by an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a cyclohexylene group having 8 to 12 carbon atoms, or is terminated by it) Represents an alkylene group). } Of benzotriazole represented by
The benzotriazole loses less than 0.22 absorbance units after 1200 hours exposure in a xenon arc weatherometer, or less than 0.27 absorbance units after 1500 hours exposure, or after 2500 hours exposure. It relates to a composition that exhibits enhanced durability and a low loss rate when the coating is exposed to actinic radiation, as evidenced by a loss of less than 0.40 absorbance units.
[0010]
Preferably component (b) is of formula A ′
Embedded image
(Where
G2Is a fluorine atom, a chlorine atom, a cyano group, RThreeSO2-, CFThree-, -CO-GThree, -COO-GThreeOr -CO-N (GThree)2Represents;
GThreeRepresents an alkyl group having 1 to 12 carbon atoms;
R1Has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or a phenyl ring substituted with 1 or 2 alkyl groups having 1 to 4 carbon atoms Represents the above-mentioned phenyl group or phenylalkyl group;
R2Is an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms, or —CH2CH2COOGFour(Where GFourIs substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, interrupted by 1 to 6 —O— atoms or substituted by OH and 1 to 6 — Represents the above alkyl group interrupted by an O-atom, and
RThreeRepresents an aryl group substituted with 1 or 2 alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkyl groups having 1 to 4 carbon atoms. ).
[0011]
  The present invention is particularly a coating composition stabilized with benzotriazole, wherein the coating composition exhibits enhanced durability and low loss rate when the benzotriazole is incorporated into the composition;
  (A) thermosetting acrylic melamine resin or acrylic urethane resin, and
  (B) 0.01 to 5% by weight of formula A based on resin solids '
[Chemical 3]
  (Where
  G 2 Is a fluorine atom, a chlorine atom, a cyano group, R Three SO 2 -, CF Three -, -CO-G Three , -COO-G Three Or -CO-N (G Three ) 2 Represents;
  G Three Represents an alkyl group having 1 to 12 carbon atoms;
  R 1 Has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms or a phenyl ring substituted with 1 or 2 alkyl groups having 1 to 4 carbon atoms Represents the above-mentioned phenyl group or phenylalkyl group;
  R 2 Is an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms, or —CH 2 CH 2 COOG Four (Where G Four Is substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, interrupted by 1 to 6 —O— atoms or substituted by OH and 1 to 6 —O -Represents an alkyl group as described above interrupted by an atom, and
  R Three Represents an aryl group substituted with 1 or 2 alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkyl groups having 1 to 4 carbon atoms. Benzotriazole represented by
  The benzotriazole is less than 0.22 absorbance units after 1200 hours exposure in a xenon arc weatherometer, or less than 0.27 absorbance units after 1500 hours exposure, or after 2500 hours exposure. It relates to a composition that exhibits enhanced durability and a low loss rate when the coating is exposed to actinic radiation, as evidenced by a loss of less than 0.40 absorbance units.
  Most preferably, in the compound of formula A ′:
  G2Is fluorine atom, chlorine atom, cyano group, RThreeSO2-, CFThree-, -COO-GThreeOr -CO-N (GThree)2Represents;
  GThreeRepresents an alkyl group having 1 to 8 carbon atoms;
  R1Represents a hydrogen atom, a phenyl group or an α-cumyl group;
  R2Represents an alkyl group having 4 to 12 carbon atoms or a phenyl group, and
  RThreeRepresents a phenyl group or an alkyl group having 8 to 12 carbon atoms.
[0012]
Particular preference is given to compounds of the formula A ′
G2Is phenyl-SO2-, Octyl-SO2-, Fluorine atom or CFThree-Represents;
R1Represents an α-cumyl group or a phenyl group, and
R2Represents a tert-butyl group or a tert-octyl group.
[0013]
Preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Examples of various substituents are as follows:
R1Or Rtwenty oneWhen any of these is an alkyl group, such a group is, for example, methyl group, ethyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, tert-amyl group, 2-ethylhexyl group, tert-octyl group, lauryl group, tert-dodecyl group, tridecyl group, n-hexadecyl group, n-octadecyl group and eicosyl;
Where any of the above groups is an alkenyl group, such a group is, for example, an allyl group or an oleyl group;
When any of the above groups is a cycloalkyl group, such groups are, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group;
When any of the above groups is a phenylalkyl group, such groups are, for example, benzyl, phenethyl, α-methylbenzyl and α, α-dimethylbenzyl groups; and
When any of the above groups is an aryl group, they are, for example, a phenyl group, a naphthyl group, or when substituted with an alkyl group, for example, a tolyl group and a xylyl group.
R6-OR is interrupted by one or more -O- groups and / or substituted by one or more OH6Part is for example-(OCH2CH2)wOH or-(OCH2CH2)wORtwenty oneIn which w represents 1 to 12 and Rtwenty oneCan be an alkyl group having 1 to 12 carbon atoms.
[0015]
When E is an alkylene group, they are a methylene group, an ethylene group, a tetramethylene group, a hexamethylene group, a 2-methyl-1,4-tetramethylene group, an octamethylene group, a decamethylene group and a dodecamethylene group;
When E is a cycloalkylene group, it is, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group and a cyclododecylene group;
And when E is interrupted or terminated by a cyclohexylene group, it is, for example, a saturated diyl group derived from limonene, referred to herein as a dihydrolimonene diyl group.
[0016]
Another preferred embodiment of the present invention is a compound of formula C, wherein R1Represents a tert-butyl group, n represents 1, RThreeRepresents a phenyl group and RFiveIs -OR6(Wherein R6Represents a linear or substituted octyl group. ). Yet another preferred embodiment of the present invention is where n represents 2 and R1Represents a tert-butyl group and RThreeRepresents a phenyl group and RFiveIs -O-R9-O- (wherein R9Is —O— or —CH2-CHOH-CH2-O-R14-O-CH2-CHOH-CH2An alkyl group having 2 to 24 carbon atoms interrupted by-. ) Represents a compound of formula C.
When E is an alkylene group, they are a methylene group, an ethylene group, a tetramethylene group, a hexamethylene group, a 2-methyl-1,4-tetramethylene group, an octamethylene group, a decamethylene group and a dodecamethylene group;
When E is a cycloalkylene group, it is, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group and a cyclododecylene group;
And when E is interrupted or terminated by a cyclohexylene group, it is, for example, a saturated diyl group derived from limonene, referred to herein as a dihydrolimonene diyl group.
[0017]
When the compound of the present invention contains a carboxyl moiety (in that case, R2Is -CH2CH2COOR6(Wherein R6Represents a hydrogen atom. ). ), Alkali metal salts or amine salts of the above acids are also considered as part of the present invention and such UV absorbers can be used in aqueous systems due to the increased water solubility of the compounds in question.
[0018]
R6, R7And R8Is —O—, —S— or —NR11The alkyl group having 3 to 16 carbon atoms which may be interrupted by-and substituted with OH may be: methoxyethyl group, ethoxyethyl group, butoxyethyl group, butoxypropyl group, methylthioethyl group, CHThreeOCH2CH2OCH2CH2-, CHThreeCH2OCH2CH2OCH2CH2-, CFourH9OCH2CH2OCH2CH2-, Ethylthiopropyl group, octylthiopropyl group, dodecyloxypropyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, -CH2CH2-NH-CFourH9, -CH2CH2CH2NH-C8H17And -CH2CH2CH2-N (CHThree) -CH2CH (C2HFive) CFourH9It is.
[0019]
R6, R7, R8, R11And R12Can be a cycloalkyl group having 5 to 12 carbon atoms: cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group or cyclodecyl group.
[0020]
R7, R8And R11Can be the following alkenyl groups: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.
[0021]
R6Is an alkenyl group, it is R as an alkenyl group.7, R8And R11Can have the same meaning as But it is -CH = CH2, N-undec-10-enyl group or n-octadec-9-enyl group, and R6Can be substituted by —OH.
[0022]
R7And R8May be the following aralkyl group having 7 to 15 carbon atoms: benzyl group, α-phenethyl group, 2-phenethyl group or 4-tert-butylbenzyl group.
[0023]
R11, R13Or R12When are aralkyl groups, they are independently of each other R7Or R8Can have the same meaning as
[0024]
Independently of each other, R7, R8And R11May be an aryl group having 6 to 14 carbon atoms: a phenyl group, an α-naphthyl group or a β-naphthyl group.
[0025]
R7And R8When is a hydroxyalkyl group having 1 to 3 carbon atoms, they are the following groups: hydroxymethyl group, 2-hydroxyethyl group or 2-hydroxypropyl group.
[0026]
As an alkylene group having 2 to 8 carbon atoms, R9And R14Can be the following groups: ethylene, propylene, butylene, hexylene or octylene.
[0027]
R as an alkylene groupTenMay be the same group, but additionally may be a higher molecular weight group such as a decylene group or a dodecylene group.
[0028]
R9When is an alkenylene group having 4 to 8 carbon atoms, the following are examples of suitable groups: butenylene group.
[0029]
R9And R14In this case, an appropriate group of a linear or branched alkylene group having 4 to 10 carbon atoms interrupted by -O- is shown below: -CH2CH2OCH2CH2-, -CH (CHThree) -CH2-O-CH2-CH (CHThree) -CH2CH2OCH2CH2OCH2CH2-And -CH2CH2OCH2CH2OCH2CH2OCH2CH2-.
[0030]
R14When is a cycloalkylene group, the following groups are included: 1,3-cyclohexylene group and 1,4-cyclohexylene group.
[0031]
R14When is an arylene group, this is in particular the following group: 1,3-fu, nylene group or 1,4-phenylene group.
[0032]
As an alkylene group having 2 to 12 carbon atoms, Z is a straight chain or branched chain. For example, ethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, dodecamethylene group, 1,1-ethylidene group, 2,2-propylidene group, 2,2-amylidene group or 2-ethylhexa A methylene group. An alkylene group having 2 to 6 carbon atoms is preferred.
[0033]
When Z is an alkylene group having 4 to 12 carbon atoms interrupted by oxygen, it is for example: —CH2-CH2-O-CH2-CH2-, -CH2-CH2-O-CH2-CH2-CH2-, -CH2-CH2-O-CH2-CH2-O-CH2-CH2-Or -CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2-And the alkylene group is a nitrogen atom, the group -N (R16)-(Wherein R16Is defined the same as above. ), For example, -CH2-CH2-NH-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-NH- (CH2)8-Or -CH2-CH2-CH2-N (CHThree) -CH2-CH (C2HFive) (CH2)Four-.
[0034]
As an alkylene group of 3 to 12 carbon atoms substituted by a hydroxyl group, Z is a 2-hydroxytetramethylene group, a 2-hydroxyhexamethylene group, and in particular a 2-hydroxytrimethylene group.
[0035]
Z as the cyclohexylene group is, for example, a 1,4-cyclohexylene group, in particular, a 1,2-cyclohexylene group.
[0036]
Z as the phenylene group is, for example, an m-phenylene group or a p-phenylene group.
[0037]
m can be 0, 1 or 2, but it is preferably 2.
[0038]
p is preferably 1, but can also be 0 if both X and Y are bound by nitrogen.
[0039]
R as an alkyl group having 1 to 8 carbon atoms1For example: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, tert-amyl group, n-hexyl group, n- A heptyl group, an n-octyl group, a 2-ethylhexyl group, or a tert-octyl group. A tert-butyl group is preferred.
[0040]
R as an alkyl group having 1 to 12 carbon atoms16, R17And R20Is the above-mentioned R1It has the same meaning as given for and is additionally a linear or branched nonyl, decyl, undecyl or dodecyl group.
[0041]
R16And R17When is an alkyl group interrupted by an oxygen atom, the applicable examples are the same as those described in the above sentence for Z.
[0042]
R as an aralkyl group16And R17Examples of are: benzyl, α-methylbenzyl, 1-phenylethyl, α, α-dimethylbenzyl or 1-phenylpropyl.
[0043]
When Z is an ethylene group, R16And R17Together form an ethylene group, which is equivalent to cross-linking with a piperazine group.
[0044]
Y is a group -N (R17)-, R15And R17Together form the group —CO—CH═CH—CO—, thus the group —X— (Z)p-Substituent on
Embedded image
Form.
[0045]
However, R15Is preferably -CO-C (R18) = CHR14And R18And R19Is preferably a methyl group and in particular a hydrogen atom.
[0046]
R2Is -CH2-CH2-CO-O-C (G) = CH2And G represents a hydrogen atom or a methyl group.
[0047]
The present invention also includes formulas I, II, III or IV
Embedded image
{Where
G1Represents a hydrogen atom or a halogen atom;
G2Is a cyano group, EThreeSO-, EThreeSO2-, -COOGThree, CFThree-, -P (O) (C6HFive)2, -CO-GThree, -CO-NH-GThreeOr -CO-N (GThree)2Represents;
GThreeIs a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 7 carbon atoms. A phenylalkyl group having 15 to 15 phenyl, a phenyl group, the phenyl group substituted with 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring;
E1Represents a hydrogen atom, a phenylalkyl group having 7 to 15 carbon atoms, a phenyl group, the above phenyl group substituted with 1 to 4 alkyl groups having 1 to 4 carbon atoms on the phenyl ring, or the above phenylalkyl group;
E2Is a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or 7 carbon atoms. Represents a phenylalkyl group having 15 to 15 phenyl groups, a phenyl group, the phenyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms on the phenyl ring,
Or E2Is a hydroxyl group or -OEFour(Where EFourRepresents a linear or branched alkyl group having 1 to 24 carbon atoms. ); One or more -OH, -OCO-E11, -OEFour, -NCO or -NH2Or an alkyl group substituted by a mixture thereof; or one or more —O—, —NH—, or —NEFour-Interrupted by groups or mixtures thereof and unsubstituted or one or more -OH, -OEFourOr -NH2Represents the above alkyl group or the above alkenyl group optionally substituted by a group or a mixture thereof;
Or E2Is -SEThree, -NHEThreeOr -N (EThree)2 Or
Or E2Is-(CH2)m-CO-X- (Z)p-Y-E15
[In the formula, X represents —O— or —N (E16)-
Y represents —O— or —N (E17)-
Z represents an alkylene group having 2 to 12 carbon atoms, 1 to 3 nitrogen atoms, an oxygen atom, or an alkylene group having 4 to 12 carbon atoms interrupted by a mixture thereof, or 3 to 12 carbon atoms. An alkylene group, butenylene group, butynylene group, cyclohexylene group or phenylene group, each of which is substituted with a hydroxyl group,
m represents 0, 1 or 2;
p represents 1 or each of X and Y is —N (E16)-And -N (E17) Also represents 0,
E15Is a group -CO-C (E18) = C (H) E19Or Y is -N (E17)-Represents E17Together with the group -CO-CH = CH-CO-
E18Represents a hydrogen atom or a methyl group,
And E19Is a hydrogen atom, a methyl group or -CO-X-E20Represents
E20Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a formula
Embedded image
(In the formula, symbol G1, G2, E1, X, Z, m and p have the above definitions. )
And E16And E17Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 12 carbon atoms interrupted by 1 to 3 oxygen atoms, or a cyclohexyl group or 7 carbon atoms. Represents 15 to 15 aralkyl groups,
And E when Z represents an ethylene group16Is E17Together with it forms an ethylene group. ];
n represents 1 or 2,
If n represents 1, then EFiveIs Cl, OE6Or NE7E8Or
EFiveIs -PO (OE12)2, -OSi (E11)ThreeOr -OCO-E11Or -O-, -S- or -NE11Interrupted by -unsubstituted or -OH or -OCO-E11A linear or branched alkyl group having 1 to 24 carbon atoms, which may be substituted by: an unsubstituted or cycloalkyl group having 5 to 12 carbon atoms substituted by —OH; A straight-chain or branched alkenyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, substituted with —OH, —CH2-CHOH-E13Or represents a glycidyl group;
E6Is a hydrogen atom, unsubstituted or one or more OH, OEFourOr NH2Represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms substituted by a group, or -OE6Is-(OCH2CH2)wOH or-(OCH2CH2)wOEtwenty oneWherein w represents 1 to 12 and Etwenty oneRepresents an alkyl group having 1 to 12 carbon atoms);
E7And E8Independently of one another, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms; -O-, -S- or -NE11A straight or branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aryl group having 1 to 3 carbon atoms interrupted by- Represents a hydroxyalkyl group, or
E7And E8Represents, together with the N atom, a pyrrolidine ring, piperidine ring, piperazine ring or morpholine ring;
If n represents 2, then EFiveIs a divalent group -OE9-O- or -N (E11-ETen-N (E11)-Represents one of;
E9Is an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 4 to 8 carbon atoms, an alkynylene group having 4 carbon atoms, a cyclohexylene group, —O— or —CH.2-CHOH-CH2-OE14-O-CH2-CHOH-CH2Represents a linear or branched alkylene group of 4 to 10 carbon atoms interrupted by-
ETenIs a linear or branched alkylene group having 2 to 12 carbon atoms which may be interrupted by -O-, cyclohexylene group or
Embedded image
Or
Or ETenAnd E11Together with two nitrogen atoms forms a piperazine ring,
E14Is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 4 to 10 carbon atoms interrupted by —O—, a cycloalkylene group, an arylene group, or
Embedded image
Represents
E7And E8Each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or E7And E8Together represent an alkylene group having 4 to 6 carbon atoms, a 3-oxapentamethylene group, a 3-iminopentamethylene group or a 3-methyliminopentamethylene;
E11Is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a straight chain or branched chain alkenyl group having 3 to 8 carbon atoms, carbon Represents an aryl group having 6 to 14 atoms or an aralkyl group having 7 to 15 carbon atoms;
E12Is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. Represents an aryl group of 16 to 16 or an aralkyl group of 7 to 15 carbon atoms;
E13Is H, -PO (OE12)2A straight-chain or branched alkyl group having 1 to 18 carbon atoms, an unsubstituted or substituted phenyl group with OH, an aralkyl group having 7 to 15 carbon atoms, or —CH2OE12Represents;
EThreeIs an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a 7 to 15 carbon atom. A phenylalkyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group or perfluoroalkyl moiety substituted by one or two alkyl groups having 1 to 4 carbon atoms, having 6 to 16 carbon atoms; Represents a certain 1,1,2,2-tetrahydroperfluoroalkyl group;
L represents an alkylene group having 1 to 12 carbon atoms, an alkylidene group having 2 to 12 carbon atoms, a benzylidene group, a p-xylylene group or a cycloalkylidene group, and
T is -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO- or -CO-NGFive-E-NGFive-CO- (wherein E is interrupted by an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or a cyclohexylene group having 8 to 12 carbon atoms, or a terminal group thereof) Represents an alkylene group, and GFiveIs GThreeOr represents a hydrogen atom. );
However, G2Is EThreeSO- or EThreeSO2If-, E1Is not a phenylalkyl group. } Is also related to the novel benzotriazoles represented by
[0048]
Preferably, the novel benzotriazoles have the formula I ′
Embedded image
(Where
G2Is a cyano group, EThreeSO2-, CFThree-, -COO-GThree-CO-NHGThreeOr -CO-N (GThree)2Represents;
GThreeRepresents an alkyl group having 1 to 12 carbon atoms;
E1Represents a hydrogen atom, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms, or the above phenyl group or phenylalkyl group substituted on the phenyl ring by 1 or 2 alkyl groups having 1 to 4 carbon atoms. ;
E2Is an alkyl group having 1 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 15 carbon atoms, or —CH2CH2COOGFour(Where GFourIs substituted by a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or OH, interrupted by 1 to 6 —O— atoms or substituted by OH and 1 to 6 — Represents the above alkyl group interrupted by an O-atom, and
EThreeRepresents an aryl group having 8 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, or the above aryl group substituted by 1 or 2 alkyl groups having 1 to 4 carbon atoms; and
G2Is EThreeSO- or EThreeSO2If-, E1Is not a phenylalkyl group. )
[0049]
Most preferably, in formula I ′:
G2Is a cyano group, EThreeSO2-, CFThree-, -COO-GThreeOr -CO-N (GThree)2Represents;
GThreeRepresents an alkyl group having 1 to 8 carbon atoms;
E1Represents a hydrogen atom, a phenyl group or an α-cumyl group;
E2Represents an alkyl group of 4 to 12 carbon atoms, and
EThreeRepresents a phenyl group or an octyl group, and
However, G2Is EThreeSO2-If-1Is not a α-cumyl group.
[0050]
  Particularly preferred is the compound of formula I ′
  G2Is CFThree-Represents;
  E1Represents an α-cumyl group or a phenyl group, and
  E2Represents a tert-butyl group or a tert-octyl group.
  Furthermore, the present invention particularly relates to the formula I '
[Chemical 2]
  (Where
  G 2 Is CF Three -Represents;
  E 1 Represents a hydrogen atom or an α-cumyl group;
  E 2 Represents an alkyl group having 4 to 12 carbon atoms. ).
[0051]
  The present invention also includes (a) an organic material that undergoes heat, oxidation or light induced decomposition, and
  (B) an effective stabilizing amount of a compound of formula I, II, III or IV
It also relates to a composition stabilized against heat, oxidation or light-induced degradation.
  BookThe invention in particular comprises (a) a thermosetting acrylic melamine resin or acrylic urethane resin, and
  (B) Formula I ' Effective stabilizing amount of the compound represented by
A composition stabilized against heat, oxidation or light-induced degradation.
[0052]
Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, in particular a thermoplastic polymer.
[0053]
Most preferably, the polymer is a polyolefin or polycarbonate, in particular polyethylene or polypropylene; most particularly polypropylene.
[0054]
In another preferred embodiment of the present invention, the organic material is a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin having a carbamate side group crosslinked with melamine or a melamine containing a carbamate group. And a resin selected from the group consisting of crosslinked acrylic polyol resins.
[0055]
Most preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.
[0056]
Still in another preferred embodiment of the invention, the organic material is a recording material.
[0057]
The recording material of the present invention is suitable for pressure sensitive copying systems, photographic copying systems using microcapsules, thermal copying systems, photographic materials and ink jet printing.
[0058]
The recording material according to the invention is distinguished by an unexpected improvement in quality, in particular with respect to light fastness.
[0059]
The recording material according to the invention has a structure known for special use. They consist of conventional carriers, for example paper or plastic films that are coated with one or more layers. Depending on the type of material, these layers contain suitable necessary components, for example in the case of photographic materials, silver halide emulsions, dye couplers, dyes and the like. A material that is particularly suitable for ink jet printing has a layer that is particularly absorbent for the ink on a conventional carrier. In this case, the paper simultaneously functions as a carrier material and an ink absorbing layer. Suitable materials for ink jet printing are described, for example, in US Pat. 5,073,448 (incorporated herein by reference).
[0060]
The recording material can also be transparent, for example in the case of a projection film.
[0061]
The compounds of the formulas I, II, III or IV can be formulated in the carder material simultaneously with the manufacture of the sowing material, for example by being added to the paper pulp in the manufacture of paper. . Another method of application is to spray an aqueous solution of a compound of the formula I, II, III or IV or add the compound to the coating composition.
[0062]
Coating compositions intended for transparent recording materials suitable for transparent films must not contain light-dispersing particles such as pigments or fillers.
[0063]
Dye-binding coating compositions contain a number of other additives such as antioxidants, light stabilizers (including UV absorbers not belonging to the UV absorbers of the present invention), viscosity improvers, fluorescent enhancements. Whitening agents, biocides and / or antistatic agents can be included.
[0064]
The coating composition is usually prepared as follows: a water-soluble component such as a binder is dissolved in water and stirred together. Solid components, such as the fillers described above and other additives, are suspended in this aqueous medium. The dispersion is performed by, for example, an apparatus for an ultrasonic sample, a turbine stirrer, a homogenizer, a colloid mill, a bead mill, a sand mill, a high-speed stirrer, or the like. Compounds of formula I, II, III and IV can be easily incorporated into coating compositions.
[0065]
The recording material of the present invention is preferably 1 to 5000 mg / m.2, Especially 50-1200mg / m2Containing a compound of formula I
[0066]
As already mentioned, the recording material of the present invention covers a wide range of fields. Compounds of formulas I, II, III and IV can be used, for example, in pressure-sensitive copying systems. They are introduced to protect the microencapsulated dye precursor present in the paper from light or to protect the dye formed therein in the binder of the development layer from light. .
[0067]
A photocopying system using photosensitive microcapsules developed by pressure is described in US Pat. 4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,536,463; 4,551,407; 4,562,137 and 4,608,330; EP-A-139,479; EP-A-162,664; EP-A-164,931; EP-A-237,024; EP-A-237,025 and EP-A-260,129 Has been. In all these systems, the compounds of the present invention may be incorporated into the dye receiving layer. These compounds, however, may be incorporated in the donor layer to protect the color former from light.
[0068]
Photographic materials that can be stabilized are photographic dyes and layers containing such dyes or precursors thereof, such as photographic paper and films. Suitable materials are described, for example, in US Pat. 5,364,749 (incorporated herein by reference). The compounds of the formula I, II, III or IV here function as UV filters against electrostatic flashes. In color photographic materials, couplers and dyes are protected against photochemical degradation.
[0069]
The compounds according to the invention can be used for all types of color photographic materials. For example, they can be used for color photographic paper, color reversal photographic paper, direct positive color material, color negative film, color positive film, color reversal film and the like. They are preferably used especially for photographic color materials comprising reversal substrates or form positives.
[0070]
The color photographic recording material usually comprises a blue-sensitive and / or green-sensitive and / or red-sensitive silver halide emulsion layer on the support, and optionally a protective layer. It exists either in the sensitive / or red sensitive silver halide emulsion layer or in the layer between the green and red sensitive layers described above or in the layer above the silver halide emulsion layer.
[0071]
The compounds of the formulas I, II, III or IV can be used in recording materials based on the principles of photopolymerization, photoplasticization or microcapsule breakage, or white or with heat-sensitive and photosensitive diazonium salts, oxidants. It can also be used when leuco dyes or dye lactones with Lewis acids are used.
[0072]
In addition, they are used for dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing and in electrostatic, electrographic, electrophoretic, magnetographic and laser electrographic printing machines and pen-plotters. Can be used to Among the above, the recording material for dye diffusion transfer printing is preferably one recorded in, for example, EP-A-507,734.
[0073]
They are suitable for inks, preferably for ink jet printing, for example see US Pat. Can also be used as described in US 5,098,477 (incorporated herein by reference).
[0074]
The compounds of the present invention exhibit excellent hydrolytic stability, handling and storage stability, and excellent resistance to extractability when present in the stabilized composition.
[0075]
Methods for preparing the compounds of the present invention are described in the prior art. Most of the intermediates required for producing the compounds of the present invention are commercially available products.
[0076]
Among them, particularly preferred compounds are those in which X and Y are —O—; and in particular, both X and Y are —O—.
[0077]
In general, polymers that can be stabilized include the following polymers:
1. Polymers of monoolefins and diolefins such as polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and cycloolefins such as polymers of cyclopentene or norbornene, polyethylene (which can optionally be cross-linked) For example, high density polyethylene (HDPE), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
[0078]
Polyolefins, ie polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various methods and in particular by the following methods:
a) radical polymerization (usually under high pressure and high temperature);
b) Catalytic polymerization using a catalyst containing one or more metals of group IVb, Vb, VIb or VIII of the normal periodic table. These metals usually have one or more ligands that may be π- or σ-coordinated, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. These metal complexes may be free or fixed on a support, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used as such during the polymerization or another activator, typically an alkyl metal, metal hydride, alkyl metal halide, alkyl metal oxide or alkyl metal oxane (these metals are of the periodic table). Element Ia, IIa and / or IIIa). The activator may be advantageously modified with another ester, ether, amine or silyl ether group. These catalyst systems are commonly referred to as Phillips catalysts, standard oil Indiana catalysts, Ziegler (-Natta) catalysts, TNZ (DuPont) catalysts, metallocene catalysts or single seat catalysts (SSC).
[0079]
2. Mixtures of the polymers described in 1), such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).
[0080]
3. Copolymers of monoolefins with diolefins or with other vinyl monomers, such as ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-isobutylene copolymers, propylene-butene -1 copolymer, ethylene-butene-1 copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, propylene-butadiene copolymer, isobutylene-isoprene copolymer, Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and those with carbon monoxide Copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with 1 And their mixtures with the polymers described in (1), e.g. polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.
[0081]
4. Hydrocarbon resin (eg CFive-C9) And their hydrogenated modifications (eg tackifiers) and mixtures of polyalkylenes and starches.
[0082]
5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).
[0083]
6). Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene-maleic anhydride, Styrene-acrylonitrile-methyl acrylate; high impact mixture from styrene copolymer and another polymer such as polyacrylate, diene polymer or ethylene-propylene-diene terpolymer; and block copolymer of styrene such as styrene-butadiene-styrene, styrene- Isoprene-styrene, styrene-ethylene-butylene-styrene or styrene-ethylene-propylene-styrene.
[0084]
7. Styrene or α-methylstyrene graft copolymer, eg styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene; styrene, acrylonitrile and methyl methacrylate to polybutadiene; styrene to polybutadiene Styrene and acrylonitrile and maleic anhydride or maleimide to polybutadiene; styrene and maleimide to polybutadiene; styrene and alkyl acrylate or alkyl methacrylate to polybutadiene; styrene and acrylonitrile to ethylene-propylene-diene terpolymer; relay Or styrene and acrylonitrile on polyalkylmethacrylate; styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with the copolymers listed in 6), for example copolymers known as ABS-, MBS-, ASA- or AES-polymers blend.
[0085]
8). Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and Copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl / vinyl acetate or vinylidene chloride / vinyl acetate copolymers .
[0086]
9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; impact-modified polymethyl methacrylate, polyacrylamide and polyacrylonitrile with butyl acrylate.
[0087]
10. Copolymers of monomers mentioned in the previous section 9) with each other or with other unsaturated monomers, such as acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or acrylonitrile / Alkyl methacrylate / butadiene terpolymer.
[0088]
11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or their acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; And copolymers thereof with the olefins described in 1) above.
[0089]
12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, such as polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
[0090]
13. Polyacetals such as polyoxymethylene containing polyoxymethylene and ethylene oxide as comonomers; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
[0091]
14. Polyphenylene oxides and sulfides and mixtures of polyphenylene oxide and styrene polymers or polyamides.
[0092]
15. Polyurethanes derived from polyethers, polyesters or polybutadienes containing hydroxy end groups as one component and aliphatic or aromatic polyisocyanates as the other component and precursors thereof.
[0093]
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams. Aromatics starting from eg polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylenediamine and adipic acid Polyamides; polyamides made from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally an elastomer as modifier, for example poly (2,4,4-trimethylhexamethylene) terephthalamide or poly-m-phenyleneisophthalate Amides. Graft copolymers of the polyamide with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or graft copolymers of the polyamide with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further polyamides or copolyamides modified with EPDM or ABS. Polyamide condensed during processing (RIM-polyamide system).
[0094]
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
[0095]
18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoate, and hydroxy end groups Block copolyetheresters derived from containing polyethers; and polyesters modified with polycarbonate or MBS.
[0096]
19. Polycarbonates and polyester-carbonates.
[0097]
20. Polysulfones, polyether sulfones and polyether ketones.
[0098]
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
[0099]
22. Dry and non-dry alkyd resins.
[0100]
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, and vinyl compounds as crosslinkers, and their halogen-containing modifications with low flammability.
[0101]
24. Crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylate, urethane-acrylate or polyester-acrylate.
[0102]
25. Alkyd resin, polyester resin or acrylate resin crosslinked with melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate or epoxy resin.
[0103]
26. Crosslinked epoxy resins derived from polyepoxy, for example from bisglycidyl ether or from alicyclic diepoxides.
[0104]
27. Natural polymers such as cellulose, natural rubber, gelatin and chemically modified derivatives thereof such as cellulose acetate, cellulose propionate and cellulose butyrate, or such as cellulose ethers such as methylcellulose; and rosin And their derivatives.
[0105]
28. Mixtures (polyblends) of the aforementioned polymers, for example 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 PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.
[0106]
29. The above oils, fats based on pure monomeric compounds or natural and synthetic organic materials comprising such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) The material can be used as a fiber spinning oil for the polymer as well as an aqueous emulsion of such a material in a mixture with the mineral oil mixed with the appropriate weight ratios of styrene and wax.
[0107]
30. Aqueous emulsions of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer.
[0108]
31. For example, US Pat. A soft hydrophilic polysiloxane as described in US Pat. No. 4,259,467; Polysiloxanes such as the rigid polyorganosiloxanes described in US Pat.
[0109]
32. Polyketimine blended with unsaturated acrylic polyacetoacetate resin or unsaturated acrylic resin. Unsaturated acrylic resins include urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with side unsaturated groups, and acrylate melamine. Polyketimines are synthesized from polyamines and ketones in the presence of an acid catalyst.
[0110]
33. A radiation curable composition comprising an ethylenically unsaturated monomer or oligomer and an unsaturated aliphatic oligomer.
[0111]
34. Epoxy melamine resin, such as light stable epoxy resin, cross-linked by an epoxy functional co-etherized high solid melamine resin such as LSE 4103.
[0112]
In general, the compounds of the present invention are used in an amount of from about 0.01 to about 5% by weight of the composition to be stabilized, depending on the particular substrate and application method. An advantageous range is from about 0.05 to about 3%, and especially from about 0.05 to about 1%.
[0113]
The stabilizers of the present invention can be easily incorporated into organic polymers by conventional techniques at a convenient stage prior to the production of molded articles therefrom. For example, the stabilizer may be mixed with the polymer in the form of a dry powder, or the stabilizer suspension or emulsion may be mixed with the polymer solution, suspension or emulsion. The resulting stabilized polymer composition of the present invention optionally comprises about 0.01 to about 5% by weight, preferably about 0.025 to about 2% by weight and especially about 0.1 to 1% by weight. It may contain various conventional additives in amounts such as those listed below or mixtures thereof.
[0114]
1. Antioxidant
1.1. Alkylated monophenols, such as
2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol,
2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2- (α-methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol,
2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol.
[0115]
1.2. Alkylated hydroquinoneFor example
2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butylhydroquinone,
2,5-di-tertiary amyl hydroquinone,
2,6-Diphenyl-4-octadecyloxyphenol.
[0116]
1.3. Hydroxylated thiodiphenyl etherFor example,
2,2′-thiobis (6-tert-butyl-4-methylphenol),
2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol),
4,4'-thiobis (6-tert-butyl-2-methylphenol).
[0117]
1.4. Alkylidene bisphenol, for example
2,2′-methylenebis (6-tert-butyl-4-methylphenol),
2,2′-methylenebis (6-tert-butyl-4-ethylphenol),
2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol],
2,2′-methylenebis (4-methyl-6-cyclohexylphenol),
2,2′-methylenebis (6-nonyl-4-methylphenol),
2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol],
2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol],
2,2'-methylenebis (4,6-di-tert-butylphenol),
2,2'-ethylidenebis (4,6-di-tert-butylphenol),
2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol),
4,4'-methylenebis (2,6-di-tert-butylphenol),
4,4′-methylenebis (6-tert-butyl-2-methylphenol),
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol,
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane,
Ethylene glycol bis [3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) butyrate],
Di (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene,
Bis [2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.
[0118]
1.5. Benzylic compounds, for example
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,
3,5-Di-tert-butyl-4-hydroxybenzyl mercaptoacetic acid isooctyl ester
Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl isocyanurate,
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester,
Calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
[0119]
1.6. Acylaminophenols, for example
Lauric acid 4-hydroxyanilide,
4-hydroxyanilide stearate,
2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine,
Octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate.
[0120]
1.7. β- ( 3,5 -Esters of ditertiarybutyl-4-hydroxyphenyl) propionic acid with the following mono- or polyhydric alcohols:
Examples of alcohols: methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris (hydroxyethyl) isocyanurate, thiodiethylene glycol, N, N'-bis (hydroxyethyl) ) Oxalic acid diamide, triethanolamine, triisopropylethanolamine.
[0121]
1.8. esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with the following mono- or polyhydric alcohols:
Examples of alcohols: methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris (hydroxyethyl) isocyanurate, thiodiethylene glycol, N, N'-bis (hydroxyethyl) ) Oxalic acid diamide, triethanolamine, triisopropylethanolamine.
[0122]
1.9 β- ( 3,5 An amide of ditertiarybutyl-4-hydroxyphenyl) propionic acid,For example, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine,
N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine,
N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
[0123]
1.10. Diarylamines such as
Diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, 4,4′-di-tert-octyl-diphenylamine, N-phenylbenzylamine and 2,4,4- Reaction product of trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
[0124]
2. UV absorbers and light stabilizers
2.1. 2- (2 ' -Hydroxyphenyl ) BenzotriazoleFor example,
5'-methyl, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3 ' , 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3 ' , 5′-Di-tertiary amyl and 3 ′, 5′-bis (α, α-dimethylbenzyl) derivatives, 3′-tert-butyl-5 ′-(2- (omega-hydroxy-octa- (ethyleneoxy) ) Carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5 '-(2-octyloxycarbonyl) ethyl-, and dodecylated-5'-methyl-derivatives.
[0125]
2.2. 2-hydroxy-benzophenoneFor example
4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4 , 4'-dimethoxy derivatives.
[0126]
2.3. Substituted and unsubstituted benzoic acid estersFor example
Phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
[0127]
2.4. Acrylate, for example
α-cyano-β, β-diphenyl-acrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, α Carbomethoxy-p-methoxycinnamic acid methyl ester and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.
[0128]
2.5. Nickel compoundsFor example
Nickel complexes of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], for example 1: 1 or 1: 2 complexes, optionally n-butylamine, With other ligands such as ethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl or ethyl esters Nickel salts, nickel complexes of ketoximes such as 2-hydroxy-4-methyl-phenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally other ligands Things that involve.
[0129]
2.6 Steric hindered amineFor example
Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl- 4-hydroxybenzylmalonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinate Products of condensation with acids, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3, Condensation products with 5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2, 3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazino ), Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
[0130]
2.7 Oxalic acid diamideFor example
4,4′-di-octyl-oxy-oxanilide,
2,2'-di-octyloxy-5,5'-di-tert-butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl oxanilide, 2- Ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxanilide and the compound and 2-ethoxy- Mixtures with 2'-ethyl-5,4'-di-tert-butyl-oxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
[0131]
2.8. 2- (2-Hydroxyphenyl) -s-triazineFor example
2,6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine;
2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine;
2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine;
2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine;
2,4-bis [2-hydroxy-4- (2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-dimethylphenyl) -s-triazine;
2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) -phenyl] -6- (4-bromophenyl) -s-triazine;
2,4-bis [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine;
2,4-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine;
[0132]
3. Metal deactivatorFor example
N, N′-diphenyloxalic acid diamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis (3,5-di-tert-butyl- 4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalodihydrazide
[bis (benzylidene) oxalodihydrazide].
[0133]
4). Phosphite and phosphoniteFor example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tertiary Butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl-phenyl) pentaerythritol Diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di Tert-butylphenyl) 4,4'-biphenylene diphosphonite.
[0134]
5. Compounds that decompose peroxidesFor example
esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl ester; mercaptobenzimidazole, or
2-Zinc salt of mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.
[0135]
6). HydroxylamineFor example
N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexa N, N-dialkylhydroxylamine derived from decylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, hydrogenated tallow amine.
[0136]
7). NitronsFor example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N -Hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N -Octadecyl-α-hexadecylnitrone, a nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow.
[0137]
8). Polyamide stabilizerFor example
Copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.
[0138]
9. Basic auxiliary stabilizerFor example
Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivative, hydrazine derivative, amine, polyamide, polyurethane,
Alkali metal salts and alkaline earth metal salts of higher fatty acids such as Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate, or zinc pyrocatecholate.
[0139]
10. Nucleating agentFor example
4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
[0140]
11. Fillers and reinforcing agentsFor example
Calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
[0141]
12 Other additivesFor example
Plasticizers, lubricants, emulsifiers, pigments, brighteners, flame retardants, antistatic agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
[0142]
13. Benzofuranones and indolinonesFor example those described in US-A-4325863, US-A-4338244, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3′-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3 , 5-Dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di tert- butyl benzofuran-2-one.
[0143]
13. Co-stabilizers other than the benzofuranones listed above are added at a concentration of, for example, 0.01 to 10% with respect to the total weight of the material to be stabilized.
[0144]
Another preferred composition contains, in addition to components (a) and (b), in particular phenolic antioxidants, light stabilizers or processing stabilizers.
[0145]
Particularly preferred additives are the phenolic antioxidants listed above (item 1. above), sterically hindered amines (item 2.6 above), phosphites and phosphonites (item 4. above). It is a compound that decomposes peroxides (item 5 above).
[0146]
Also particularly preferred additional additives (stabilizers) are, for example, those described in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312. Benzofuran-2-one.
[0147]
Particularly interesting phenolic antioxidants are n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis (3,5-di-tert-butyl-4-hydroxy Hydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate Nurate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-butyl- -Hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 1,3,5-tris (2 , 6-Dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1,3,5 -Tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl ) Mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl- -Hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis [3,3-di (3-tert-butyl-4-hydroxyphenyl) butyrate], octyl 3,5-di-tert -Butyl-4-hydroxybenzylmercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl Selected from the group consisting of -4-hydroxyhydrocinnamoyloxy) -ethyl] -oxamide.
[0148]
The most preferred phenolic antioxidants are neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydro Cinnamate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-) tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2′-ethylidene-bis (4,6-di-tert-butylphenol).
[0149]
Sterically hindered amines of particular interest are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate Di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl-2,2,6 , 6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4 .5] Decane-2,4-dione, tris (2,2,6,6-tetramethyl-4-piperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,4,4-tetra Methyl -Oxopiperazin-4-yl) ethane, 2,2,6,6-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5.1.1.12] heneicosane, 2,4-dichloro Polycondensation product of -6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), 1- (2-hydroxyethyl) A polycondensation product of 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 4,4′-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and Polycondensation product with 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis 1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, 2,4-dichloro-6-morpholino-s-triazine and 4,4′- Polycondensation product with hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ′, N ″, N ″ ′-tetrakis [(4,6-bis (butyl-1, 2,2,6,6-pentamethylpiperidin-4-yl) -amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, mixed [2,2,6,6 -Tetramethylpiperidin-4-yl / β, β, β ', β'-tetramethyl-3,9,-(2,4,8,10-tetraoxaspiro [5.5] -undecane) diethyl] 1 , 2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5 .5] -undecane) diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4′-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, N-1,2 , 2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl n-dodecylsuccinimide, 1-acetyl 3-dodecyl 7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, di- (1-octyloxy-2,2,6,6-tetramethylpiperidine -4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4 -Hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) ) Imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] and 2,4,6-tris [N- (1-cycl It is selected from the group consisting of hexyl-2,2,6,6-tetramethyl-piperidin-4-yl)-n-butylamino] -s-triazine.
[0150]
The most preferred sterically hindered amines are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, 1- (2-hydroxyethyl) -2, Polycondensation product of 2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino -Condensation products with -2,2,6,6-tetramethylpiperidine), N, N ', N ", N"'-tetrakis [(4,6-bis (butyl-1,2,2,6) , 6-Pentamethylpi Lysine-4-yl) -amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, di- (1-octyloxy-2,2,6,6-tetramethylpiperidine- 4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4- Hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] or 2,4,6-tris [N- ( - cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) are -n- butylamino] -s-triazine.
[0151]
The composition of the present invention may additionally contain other ultraviolet absorbers selected from the group consisting of s-triazines, succinic anilides, hydroxybenzophenones, benzoates and α-cyanoacrylates.
[0152]
In particular, the composition of the present invention provides effective stabilization of at least one other 2-hydroxyphenyl-2H-benzotriazole; another other trisaryl-s-triazine; or a sterically hindered amine or mixtures thereof. An additional amount can be included.
[0153]
Preferably, 2-hydroxyphenyl-2H-benzotriazole is 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole; 2- [2-hydroxy-3,5-di ( α, α-dimethylbenzyl) phenyl] -2H-benzotriazole; 2- [2-hydroxy-3- (α, α-dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole; 2- {2-hydroxy -3-tert-butyl-5- [2- (omega-hydroxy-octa (ethyleneoxy) carbonyl) ethyl] phenyl} -2H-benzotriazole; and 2- {2-hydroxy-3-tert-butyl-5- [2- (Octyloxy) carbonyl) ethyl] phenyl} -2H benzotriazole is selected from the group consisting of.
[0154]
Preferably, the other tris-aryl-s-triazine is 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine; Diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do- / tri -Decyloxy-2-hydroxypropoxy) phenyl] -s-triazine and 2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6) -Tetramethylpiperidin-4-yl) amino] -s-triazine.
[0155]
Alkyd resin lacquers which can be stabilized against the action of light and moisture according to the invention are customary stoving lacquers (automobile finishing lacquers), for example alkyd / melamine and alkyd / acrylic / melamine, which are used in particular for coating automobiles. A resin-based lacquer (see H. Wagner and HF Starx, “Lackkunstarz” (1977), pages 99-123). Other cross-linking agents include glycouril resins, blocked isocyanates or epoxy resins.
[0156]
The lacquers stabilized according to the invention are suitable for both metal finish applications and solid shade finishes, especially in the case of retouch finishes, as well as various coil coating applications. The lacquer stabilized according to the invention is preferably applied according to conventional methods by either one coating layer method or by two coating layer methods. In the latter two-coat layer method, an undercoat layer containing pigment is first applied and then a coating layer of transparent lacquer is applied thereon.
[0157]
The compounds of the present invention are applied in acid-free catalytic thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicone, isocyanate or isocyanurate. It should also be noted that you get. The epoxy and the epoxy-polyester resin are crosslinked with a common crosslinking agent such as an acid, an acid anhydride, or an amine. Thus, epoxides can be utilized as crosslinkers for various acrylic or polyester resins that have been modified by the presence of reactive groups on the backbone.
[0158]
When used in dual coating layer finishes, the compounds of the present invention can be applied to either the transparent layer or both the transparent layer and the content pigment subbing layer.
[0159]
If a water soluble, water miscible or water dispersible coating is desired, an ammonium salt of the acid group present in the resin is formed. Powder coating compositions can be made by reacting selected alcohol components with glycidyl methacrylate.
[0160]
The benzotriazoles of the present invention are produced by conventional methods for producing such compounds. Conventional methods include diazotization of substituted o-nitroanilines followed by coupling of the resulting diazonium salt with a substituted phenol and reduction of the resulting azobenzene intermediate to the corresponding desired benzotriazole. The starting materials for these benzotriazoles are multi-items on the market or can be prepared by conventional methods of organic synthesis.
[0161]
The benzotriazoles of the present invention with enhanced durability are particularly suitable for automotive coating applications, but also for other applications where such enhanced durability is required for solar films, etc. It should be taken into account that it can be useful.
[0162]
【Example】
The following examples are for illustrative purposes only.
Example 1
Preparation of 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
a) Diazotization of 4-amino-3-nitro-benzotriazole
To a 500 ml three-necked flask equipped with a mechanical stirrer was added 41.2 g 4-amino-3-nitro-benzotrifluoride, 52 ml concentrated hydrochloric acid and 100 ml distilled water. The stirred solution was cooled to 5 ° C. and 17.3 g sodium nitrite dissolved in 50 ml water was added. The solution is stirred at 0-5 ° C for 2 hours, then filtered and stored at -10 ° C.
[0163]
b) Monoazo adduct
To a 1000 ml flask fitted with a mechanical stirrer is added 40 g sodium hydroxide dissolved in 200 ml methanol and 32.4 g 2-α-cumyl-4-tert-octylphenol in 50 ml xylene. The solution is cooled to 5 ° C and the diazo solution of 4-amino-nitro-benzotrifluoride prepared in a) is added at 0-5 ° C over 2 hours. Then 100 ml of xylene are added and the organic layer is washed with water, aqueous hydrochloric acid, water, aqueous sodium bicarbonate and finally water. The solvent is removed under reduced pressure and the residue is purified by chromatography (silica gel, heptane; ethyl acetate = 95: 5) to give 42.1 g of the addition product as a dark red paste.
[0164]
c) Reduction of monoazo adduct
A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 ml of water, 42.1 g of the monoazo adduct prepared in b) and 400 ml of ethanol. The mixture is heated to 80 ° C. and 27 g of formamidine sulfinic acid is added in portions with stirring. After 1.5 hours, the solution is cooled to room temperature and 100 ml of water is added. The pH is adjusted to pH 7 with concentrated hydrochloric acid. Ethanol is distilled off under reduced pressure, and the aqueous layer is extracted with methylene chloride. The solvent is then evaporated in vacuo, the residue is purified by chromatography (silica gel, heptane: toluene = 9: 1) and crystallized from ethanol. The title compound is obtained in a yield of 5.6 g as a pale yellow solid that melts at 119-121 ° C.
[0165]
Example 2
Preparation of 5-fluoro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared according to the general method of Example 1 using 31.2 g of 4-fluoro-2-nitroaniline. In part c), an additional 9 g of formamidine sulfinic acid is required to complete the reduction. Purification of the crude product on silica gel (heptane: toluene = 1: 1) gives 4.5 g of the title compound as an off-white solid. Subsequent purification by recrystallization from acetonitrile: toluene yields 1.1 g of the title compound melting at 93-96.degree.
[0166]
Example 3
Preparation of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
Perform part b) of the general method of Example 1 to prepare the monoazo intermediate of the title compound from 339.3 g of 4-chloro-2-nitroaniline. The crude product is purified by recrystallization from methanol to give 70.9 g of a deep red monoazo intermediate.
[0167]
c) Reduction of monoazo adduct
A mixture of 11.8 g sodium hydroxide and 138 g 2-butanol is heated to 95 ° C. A solution of 60.1 g of the above monoazo adduct and 1.3 g of 2,3-dichloro-1,4-naphthoquinone in 90 g of 2-butanol is added over 90 minutes with stirring. The reaction mixture is heated to remove 2-butanone byproduct with additional 2-butanol added to replace the distillate. The reaction mixture is cooled to 85 ° C., washed with 2.5N sulfuric acid and brine, and then concentrated. The residue is recrystallized from methanol: xylene to give 45.6 g of the title compound as a pale yellow solid that melts at 104-105 ° C.
[0168]
Example 4
Preparation of 5-phenylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
A stirred mixture of 75 g of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 105 g of N-methylpyrrolidone heated to 90 ° C. First, 44.3 g of 45% aqueous potassium hydroxide is added over 15 minutes, then 20.4 g of thiophenol is added over an additional 15 minutes. The reaction mixture is then heated to 170-175 ° C. for 4 hours, during which time water is removed by distillation. After cooling to 100 ° C., xylene and water are added and the resulting mixture is acidified with 15% aqueous hydrochloric acid. The organic layer is separated, washed with water and concentrated. The crude product residue is recrystallized from methanol to give 82 g of the title compound as a pale yellow solid that melts at 124-125 ° C.
[0169]
Example 5
Preparation of 5-benzenesulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
In a 1000 mL flask, 75.2 g of 5-phenylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole, 102 g of xylene prepared in Example 4, Add 0.9 g of sodium tungstate dihydrate and 18.4 g of formic acid. The mixture is heated to 50 ° C. To this stirred mixture is slowly added 36.3 g of 50% hydrogen peroxide so that the temperature does not exceed 85 ° C. , Then add additional water and xylene. The organic layer is separated, washed with aqueous sodium sulfite, then twice with water and concentrated. The crude product residue is recrystallized from methanol to give 75.2 g of the title compound as a pale yellow solid that melts at 170-171 ° C.
[0170]
Example 6
5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The method of Example 4 was performed using 30 g of 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17.6 g of nonyl mercaptan. To produce the title compound.
[0171]
Example 7
5-nonylsulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The 5-nonylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 6 was prepared without purification of the thio intermediate. Using 7 g formic acid, 0.7 g sodium tungstate dihydrate and 17.6 g 50% hydrogen peroxide, it was oxidized to the sulfone and titled as a yellow resin exhibiting a molecular ion of m / e 631. A compound is obtained.
[0172]
Example 8
Preparation of 5-chloro-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole
Perform part a) and b) of the general method of Example 1 to prepare the monoazo intermediate for the title compound from 4-chloro-2-nitroaniline and 2-phenyl-4-tert-octylphenol . The crude product is purified by recrystallization from methanol to give a deep red monoazo adduct.
[0173]
The title compound is prepared according to the reduction method of Example 3 from 65 g of the monoazo adduct prepared above, 19.9 g of sodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoquinone. . The crude product is purified on silica gel (hexane: ethyl acetate = 5: 1) to give a fraction based on the title compound showing a molecular ion of m / e 433.
[0174]
Example 9
5-phenylthio-2- (2-hydroxy-3-phenyl-5-tert-o (Cutylphenyl) -2H-benzotriazole
The title compound is prepared according to the method of Example 4 from 20 g of the compound of Example 8, 20.4 g of 45% aqueous potassium hydroxide, 10.3 g of thiophenol and 100 g of N-methylpyrrolidone. The title compound is an oil purified by chromatography on silica gel using toluene as the eluent.
[0175]
Example 10
Preparation of 5-benzenefursulfonyl-2- (2-hydroxy-3-phenyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound was obtained from 20 g of the thio compound of Example 9, 6.4 g formic acid, 15.0 g 50% hydrogen peroxide and 0.6 g sodium tungstate dihydrate according to the method of Example 5. Manufactured. Recrystallize 2.5 g of the crude material from xylene / methanol to give 2.0 g of the purified title compound as a pale yellow powder that melts at 204-206 ° C.
[0176]
Example 11
5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (the alkyl group is independently C Four , C 8 , C 12 And C 16 Manufacturing)
65.4 g of 5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, 45 mL dodecene and 13 mL methanesulfonic acid are heated to 170 ° C. under nitrogen. An additional 135 mL of dodecene is added over 4.5 hours. The reaction mixture is cooled to 100 ° C., then quenched with 400 g of crushed ice and extracted three times with ethyl acetate. The organic layers are combined, washed with water, aqueous sodium bicarbonate solution, water again and brine, dried over anhydrous magnesium sulfate and finally concentrated. The polymerizable residue is removed by bubble to bubble distillation under vacuum up to 0.2 mm and 210 ° C. Unreacted starting material is then removed by distillation (at 0.01 mm, 160 ° C.) to give 45 g of the title mixture as a yellow oil.
[0177]
Example 12
5-phenylthio-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (the alkyl group is independently C Four , C 8 , C 12 And C 16 Manufacturing)
The title mixture is prepared according to the method of Example 4 using 40 g of the mixture of Example 11, 11.2 g of potassium hydroxide and 12.3 mL of thiophenol.
[0178]
Example 13
5-benzenesulfonyl-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole (the alkyl group is independently C Four , C 8 , C 12 And C 16 Manufacturing)
A mixture of the crude product of Example 12, 350 mL isopropanol, 14.7 mL formic acid and 1.8 mL concentrated sulfuric acid is heated to reflux and 30 mL 50% hydrogen peroxide is added dropwise over 2 hours. . After an additional 3 hours at reflux, the reaction mixture is cooled and 10% sodium sulfite and aqueous sodium bicarbonate are added. Isopropanol is evaporated and the residue is extracted with methylene chloride. The organic layer is washed with water and then dried over anhydrous magnesium sulfate. Concentrate the solution to give 45 g of crude product as a viscous red yellow oil. About 30 g of this crude product is purified by chromatography on silica gel (heptane: ethyl acetate, 4: 1) to give 28.9 g of the title mixture as a yellow oil.
[0179]
Example 14
5-Diphenylphosphinyl-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole
A flame-dried 500 mL three-necked round bottom flask equipped with a condenser, magnetic stir bar and thermometer was charged with 100 mL dimethyl sulfoxide, 7.41 g (0.066 mol) potassium tert-butoxide and 11.17 g (0 .060 mol) of diphenylphosphine is added through a syringe. 10.56 g (0.030 mol) of 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole in 50 mL of dimethyl sulfoxide all together red at once Add to mixture. The resulting brown solution is stirred at 135 ° C. for 3.5 hours and then cooled to room temperature. The mixture is quenched with a portion of saturated ammonium chloride solution and ethyl acetate is added. The organic layer is separated and washed 3 times with water and once with brine, then dried over anhydrous magnesium sulfate. When 50% hydrogen peroxide is added to the solution, an exothermic reaction occurs. The mixture is left for 30 minutes, then washed once with 10% sodium pyrosulfite solution, three times with saturated sodium bicarbonate solution, once with brine and finally dried over anhydrous magnesium sulfate. The mixture is filtered through a plug of silica gel and the solvent is removed under reduced pressure to give 8.0 g of a crude yellow solid. The crude product is purified by medium pressure chromatography using heptane: ethyl acetate = 1: 1 to give 4.2 g (27% yield) of the title compound as a yellow solid melting at 98-100 ° C.
[0180]
Example 15
5-Diphenylphosphinyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
According to the method of Example 14, the title compound is used as starting benzotriazole intermediate 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole. If manufactured.
[0181]
Examples 16-26
Following the general method of Example 1, the following additional 2H-benzotriazoles of formula I ′ are prepared:
[Table 1]
[0182]
Example 27
Preparation of 5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
The title compound was prepared by carrying out the method of Example 6 using 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole and octyl mercaptan. Manufacturing.
[0183]
Example 28
Preparation of 5-octylsulfonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
5-octylthio-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 27 was prepared according to the general procedure of Example 7 without purification of the thio intermediate. The method is used to oxidize to sulfone.
[0184]
Example 29
Preparation of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole
According to part a) and b) of the general method of Example 1, the monoazo intermediate of the title compound is prepared from 17.3 g of 4-chloro-2-nitroaniline and 34.7 g of a deep red monoazo adduct Obtain a wet cake.
[0185]
Reduction of monoazo adduct
A mixture of 20 g sodium hydroxide, 500 mL water and 26.3 g monoazo adduct wet cake prepared above is heated to 30 ° C. Zinc powder (33.0 g) is added in portions over 2 hours. After this addition, 180 g of 40% aqueous sodium hydroxide is added dropwise over 1 hour. The mixture is stirred for 96 hours at ambient temperature. Zinc residues are removed by filtration. Neutralize the aqueous solution to pH 5-6 and filter the resulting slurry and filter the resulting slurry. The obtained filter cake is thoroughly dried with water and dried to obtain 22.5 g of a crude product. The crude product is purified by Soxhlet extraction using acetone to give 9.6 g of the title compound.
[0186]
Example 30
5-Chloro-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole
A mixture of 6.5 g 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 7.1 g 1-bromooctane, 5.2 g anhydrous potassium carbonate and 100 mL acetone is stirred for 24 hours. Reflux. About 100 mL of water and ethyl acetate are added to the resulting mixture and 10.6 g of crude product is isolated. Column chromatography using petroleum ether gives 0.9 g of the title compound whose structure is confirmed by Hnmr and mass spectrum.
[0187]
Example 31
Preparation of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole
Following the general method of Example 29, the title compound is prepared from 10.3 g of 4-amino-3--3-nitrobenzotrifluoride to give 6.4 g of the title compound whose structure has been determined by Hnmr. .
[0188]
Example 32
Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole
The title compound is prepared from 5.6 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole according to the general method of Example 30. The crude product is purified by column chromatography to give 1.1 g of the title compound as a white solid that melts at 79-81 ° C. Its structure is determined by Hnmr and mass spectrum.
[0189]
Example 33
Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (butoxy-2-hydroxypropoxy) phenyl] -2H-benzotriazole
2.3 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 1.3 mL of butyl glycidyl ether and 100 mg of ethyltriphenyl in Example 31 in 50 mL of xylene. The phosphonium bromide is heated to reflux under nitrogen for 14 hours. Add water (25 mL) and 25 mL of ethyl acetate and isolate 3 g of crude product.
Recrystallization from heptane gives 2.1 g of the title compound whose structure is determined by nmr.
[0190]
Example 34
Preparation of 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole
The title compound is prepared according to the general method of Example 1 and Example 29 starting from 4-amino-3-nitrobenzotrifluoride and 3-aminophenol. The product structure is determined by nmr.
[0191]
Example 35
Preparation of 5-trifluoromethyl-2- [2-hydroxy-4- (2-ethylhexanoylamino) phenyl] -2H-benzotriazole
To a mixture of 4 g 5-trifluoromethyl-2- (2-hydroxy-4-aminophenyl) -2H-benzotriazole and 1.4 g triethylamine in 75 mL toluene was added 2-ethylhexa in 125 mL toluene. Add the noyl chloride mixture dropwise. The resulting mixture is treated with 100 mL of water and the resulting crude product is purified by column chromatography to give 1.9 g of the title compound melting at 179-181 ° C. Its structure is determined by nmr.
[0192]
Example 36
Preparation of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
a) Esterification of 4-amino-3-nitrobenzoic acid
To a 2 L three-necked flask equipped with a mechanical stirrer is added 700 mL methanol, 20 g xylene, 14 g concentrated sulfuric acid and 100 g 4-amino-3-nitrobenzoic acid. The solution is heated to reflux for 33 hours. Cool the mixture to 35 ° C. and neutralize to pH 7.8. After adding water (1 L), the solid is collected and washed with 500 mL of water and dried overnight, 100.9 g of 4-amino-3-nitrobenzoic acid methyl ester is obtained.
[0193]
b) Diazotization of 4-amino-3-nitrobenzoic acid methyl ester
Into a 1 L three-necked flask equipped with a mechanical stirrer is placed 177 g of 96% sulfuric acid and then slowly added 11 g of sodium nitrite over 90 minutes. The mixture is heated to 30 ° C. to initiate the reaction. Keep temperature below 70 ° C. The mixture is then cooled to 15 ° C. and 30 g of 4-amino-3-nitrobenzoic acid methyl ester is added over 2 hours keeping the temperature between 15-20 ° C. The mixture is cooled to 0 ° C. and 200 g of ice is added to make the solution suitable for the coupling reaction to form the monoazo compound.
[0194]
c) Monoazo adduct
In a 2 L three-necked flask equipped with a mechanical stirrer and addition funnel is charged 52 g 2-α-cumyl-4-tert-octylphenol, 20 g water, 315 g methanol, 7 g xylene and 150 g sodium hydroxide. The mixture is cooled to −5 ° C. and the diazonium salt solution prepared in step b) is added over 2 hours while cooling and keeping the temperature below 3 ° C. After the diazonium salt solution is added, the pH is adjusted to 6.5-7.0. The mixture is poured into 500 mL xylene and washed 3 times with 500 mL water at 60 ° C. Xylene is removed by distillation to obtain 186 g of monoazo adduct containing residual xylene.
[0195]
d) Reduction of monoazo adduct
To a 500 mL flask equipped with a mechanical stirrer is added 186 g monoadduct prepared in step c), 125 g 2-butanol and 1.7 g 2,3-dichloro-1,4-naphthoquinone. The mixture is heated to 90 ° C. and the resulting solution is then placed in the addition funnel on the second flask. To the second flask described above is added 175 g 2-butanol and 18.6 g sodium hydroxide. The flask is heated to 95 ° C. and the monoazo solution is added over 2 hours while distilling off methyl ethyl ketone and 2-butanol. 2-Butanol (100 g) is then added and the azeotropic fraction is distilled off. The mixture is then cooled and 300 g of xylene and 200 mL of water are added. Adjust the pH to 7-7.5 using 20% sulfuric acid. The aqueous phase is separated at 60 ° C. and the organic phase is washed twice with 200 mL of water. Xylene is distilled off, and the resulting residue is recrystallized from methanol to give 8.8 g of the title compound melting at 141-143 ° C.
[0196]
Example 37
Preparation of 5-N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
a) Saponification of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
To a 250 mL three-necked flask equipped with a mechanical stirrer, thermometer, condenser and nitrogen inlet, add 1.8 g potassium hydroxide and 40 mL methanol. The mixture is heated to 40 ° C. to dissolve the potassium hydroxide. To this solution was added 2.7 g of 5-carbomethoxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in Example 36 in 40 mL of methanol. Added. The reaction mixture is refluxed for 6 hours. The mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl acetate are added, then the organic layer is separated and dried over anhydrous sodium sulfate. After vacuum stripping of the solvent, 2.5 g of 5-carboxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole is isolated.
[0197]
b) 5-chlorocarbonyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
2.5 g of 5-carboxy-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole prepared in step a) was added to a stirrer, thermometer, reflux condenser Place in a 250 mL three-necked flask equipped with a Dean-Stark trap and nitrogen inlet. Toluene (100 mL) is added and the mixture is refluxed to remove traces of water. The mixture is then cooled and 0.76 g of succinic chloride in 15 mL of toluene is added. The reaction mixture is slowly heated to 60 ° C. and kept at 60-65 ° C. for 8 hours until all the hydrogen chloride is drained to give the acid chloride of the title compound.
[0198]
c) 5-N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole
To a 500 mL flask equipped with a mechanical stirrer, drying tube, thermometer and dropping funnel, add 0.8 g di-n-butylamine, 6 mL pyridine and 25 mL toluene. The mixture is cooled to 0 ° C., the acid chloride prepared in step b) is placed in the dropping funnel and added to the reaction mixture at −5 ° C. to −10 ° C. over 30 minutes. The reaction mixture is stirred at that temperature for 1.5 hours and then kept at ambient temperature overnight. The mixture is filtered and then vacuum stripped to give 3.0 g of crude solid. The solid product is chromatographed to give 1.2 g of the title compound as a tan solid melting at 131-133 ° C. The structure is determined by nmr and mass spectrum m / z 596.
[0199]
Example 38
5-Trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole
The title compound is prepared from the diazo compound of 4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol according to the general method of Example 1, and the title compound is purified by chromatography on silica gel. Recrystallization of the product from either heptane or methanol gives the title compound as an almost white solid that melts at 80-81 ° C.
[0200]
Example of Use 39
In order to confirm the thermal durability and loss rate of various 2H-benzotriazole UV absorbers substituted with various electron-withdrawing groups or electron-donating groups from high solid thermosetting acrylic coatings, the following tests were conducted. carry out.
[0201]
The high solid thermosetting acrylic transparent paint is produced by mixing an experimental acrylic polyol resin and hexamethoxymethylmelamine ((registered trademark) Regimen 747, Monsanto) at a solid content ratio of 60/40. Add 0.7% by weight of dodecylbenzene sulfonic acid catalyst (®Nacure 5225, King Industries). Flow aid (R) Modaflow is added at 0.25 wt% to form a model acrylic melamine resin system.
[0202]
Dilute the model clear paint with xylene to a viscosity of 26-27 seconds using a Zahn # 2 cup and use 50 psi (3.5 Kg / cm2) using normal air spray.2) To 1 ″ × 3 ″ (2.54 cm × 7.62 cm) quartz slides. Curing involves baking the slides at 260 ° F. (127 ° C.) for 30 minutes. The clear paint is stabilized with 1% by weight of a hindered amine light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (registered trademark) TINUVIN 123, Ciba-Geigy) It is. Various test benzotriazole UV absorbers are blended at 5 mmol% by weight in a clear paint. The thickness of the coating on the quartz slide ranges from 1.15 to 1.41 mils (0.029 to 0.036 mm).
[0203]
The film on the crystal slide is exposed using an internal crystal and an external borosilicate S-type filter in a xenon arc weatherometer with a controlled irradiance at 6500 W according to the following conditions: To do. The irradiation cycle is as follows: linear irradiation without water spray for 40 minutes, followed by 20 minutes of light plus front spray, followed by 60 minutes of light irradiation and finally 60 minutes of ejection (dart ) Plus rear spray. Setting is 0.55 W / M at 340 nm21.98 kJ / hour. In the photoperiod, the temperature of the black panel is controlled at 70 ± 2 ° C. The relative humidity in the light cycle is in the range of 50-55% and in the dark cycle is 100%. The absorbance of the long wavelength UV band as a function of xenon arc exposure time is listed in the table below.
[0204]
In order to track the loss of UV absorber from the clear coating, the UV spectrum is measured at the beginning and at regular time intervals after exposure. The UV spectrophotometer measures absorbance linearly to 5.5 absorbance units using a reference beam attenuation technique.
[0205]
It is assumed that degradation products from UV absorbers do not contribute to the UV spectrum. This is tested by following the ratio of absorbance between the absorption band at about 300 nm and the absorption band at 340 nm. This ratio does not change when the sample is exposed. This implies that the UV spectrum of the exposed film (coating film) corresponds to the amount of UV absorber remaining in the film, but the photodegradation contributes very little to the spectrum. Yes.
[0206]
The data in the table below shows the structural formula A (where G is 1211 hours after exposure of the clear coating containing the test benzotriazole UV absorber).1Is H. ).
[Table 2]
[0207]
Reviewing these data draws some clear conclusions about the photostability of 2H-benzotriazoles and the nature of the substituents that affect the photostability.
[0208]
The increased stability is R1Is a cumyl group or a phenyl group and G2Is an electron withdrawing group such as a phenylsulfonyl group or a cyano group.
[0209]
R2The nature of the group has little effect on the light stability of the benzotriazole UV absorber.
[0210]
From these observations, the idealized benzotriazole UV absorber is G2Is an electron withdrawing group and R1Is an effective bulky group and R2Can be theoretically designed when is a thermally stable part. One such idealized compound is G2Is a phenylsulfonyl group, R1Is an α-cumyl group and R2Is benzotriazole, which is a tert-octyl group. This benzotriazole is generally described in US Pat. No. 5,280,124. The data described in Example 40 below confirms this prediction and demonstrates that this “idealized” compound actually has a much lower rate of loss than the state of the art.
[0211]
Use Example 40
  In accordance with the general method of Use Example 39, additional benzotriazole test compounds were added in a high solid thermoset acrylic melamine resin to give equivalent molar concentrations of test benzotriazole in equivalent film thickness and the first Formulated at a concentration between 1.93 wt% and 3 wt% so that the absorbance was sufficient to be about 2.0 units.
[0212]
The test disc is x180 cycles (0.45 watts / M2) In a xenon-arc weatherometer. The initial UV absorbance is measured, then the first 2000 hours at intervals of about 250 hours and thereafter every 500 hours. Each transparent coating also contains 1% by weight of a hindered amine light stabilizer, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
[0213]
The data in the table below shows the formula A (where G is the value after exposure of the transparent coating containing the test benzotriazole UV absorber for 1253 hours.1Is a hydrogen atom. ).
[Table 3]
[0214]
The data in the table below shows the formula A (wherein G) after exposing the clear coating containing the test benzotriazole UV absorber for 1489 hours.1Is a hydrogen atom. ).
[Table 4]
[0215]
The data in the table below shows the formula A (where G is the value after exposure of the clear coating containing the test benzotriazole UV absorber for 2521 hours.1Is a hydrogen atom. ).
[Table 5]
[0216]
From the above three tables, it is clear that compounds S and especially T having an electron withdrawing group on the benzo ring are significantly superior to benzotriazoles having no such group on the benzo ring.
[0217]
The data in the table below shows the formula A (wherein G, after exposure of the clear coating containing the test benzotriazole UV absorber for 1264 hours.1Is a hydrogen atom. ).
[Table 6]
[0218]
The data in the table below shows the formula A (wherein G) after exposing the clear coating containing the test benzotriazole UV absorber for 1518 hours.1Is a hydrogen atom. ).
[Table 7]
[0219]
The data in these tables show that benzotriazoles substituted on the benzo ring with groups such as electron withdrawing groups, especially trifluoromethyl groups or phenylsulfonyl groups, were measured after exposure to actinic radiation. In particular, the low loss of the absorbance value indicates that it is particularly durable. Compounds S, U, V and W are particularly durable and are consistent with the profile suggested above. Indeed, the prediction that Compound U is particularly durable has been born from the above data. A review of the data for compounds T and U is R1Compared to a mere alkyl moiety such as a tert-butyl group at1It shows the additional advantageous effect of having an effective bulky group such as an α-cumyl group at the position.

Claims (2)

  1. Formula I '
    (Where
    G 2 is C F 3 - represents;
    E 1 represents a hydrogen atom or an α-cumyl group ;
    E 2 is to display the alkyl group of 12 from 4 carbon atoms. The compound represented by this.
  2. Against heat, oxidation or light-induced degradation comprising (a) a thermosetting acrylic melamine resin or acrylic urethane resin, and (b) an effective stabilizing amount of the compound represented by formula I ′ according to claim 1 . Stabilized composition.
JP32209797A 1996-11-07 1997-11-07 Benzotriazole UV absorber with enhanced durability Expired - Lifetime JP4126364B2 (en)

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