CA2035600C - Light-stabilised binders for coating compositions - Google Patents

Light-stabilised binders for coating compositions Download PDF

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CA2035600C
CA2035600C CA 2035600 CA2035600A CA2035600C CA 2035600 C CA2035600 C CA 2035600C CA 2035600 CA2035600 CA 2035600 CA 2035600 A CA2035600 A CA 2035600A CA 2035600 C CA2035600 C CA 2035600C
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composition according
component
copolymer
hydroxyphenyl
absorber
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CA2035600A1 (en
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Andreas Valet
Roger Meuwly
Mario Slongo
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The stabilised binder is a mixture of two copolymers and at least one curing agent. The one copolymer contains fluorine or silicon and a UV absorber in copolymerised form. The other copolymer is an acrylic resin. Suitable curing agents are melamine resins or polyisocyanates.

Description

~~n~;~,n ,y, ~~~:~~t3~sJ

A-17955 +
Light-stabilised binders for coating compositions The present invention relates to a mixture of two copolymers and at least one curing agent.
The one copolymer contains fluorine or silicon and a UV absorber in copolymerised form.
The other copolymer is an acrylic resin. The mixture can be used as binder for weather-resistant coating compositions.
Coating compositions for outdoor applications often contain acrylic resins as binders because they are relatively weather-resistant. Such binders are normally copolymers of different acrylic or methacrylic acid derivatives. Light stabilisers such as UV absorbers or sterically hindered amines or both can be added to enhance weatherability (q.v.
US-A-4 314 933).
Recently, fluorine-containing binders for coating compasitions have been disclosed, for example copolymers of chlorotrifluoroethylene with vinyl ethers. These developments are described, for example, in Progress in Orgarizc Coatings 16 (1988), 113-134, ( q.v. also US-A-4 576 977). Coating compositions based on such fluorinated resins not only have excellent weatherability, but also high gloss and dirt resistance. Their drawback is the high cost of organofluorine materials. The same applies to silicon-containing binders such as silicon resins.
It has therefore already been proposed to blend such fluorine- or silicon-containing copolymers with acrylic resins, which acrylic resins have a greater solubility in solvents than the fluorine- or silicon-containing copolymers (q.v. (GB-A-2 192 399).
It has now been found that the weatherability of such binder systems can be further appreciably enhanced by incorporating in the fluorine- or silicon-containing copolymer a UV absorber by copolymerisation.
Accordingly, the present invention relates to a composition comprising (a) a fluorine- or silicon-containing copolymer; (b) a (meth)acrylic copolymer, and (c) at least one curing agent, each of which two said copolymers contains functional groups which are able to r~,~~, ~~~'~ ~< ~~
react with the curing agent, wherein component (a) contains a UV absorber in copolymerised form.
Suitable functional groups are typically hydroxyl, carboxyl, anhydride or epoxy groups.
Preferably both copolymers contain hydroxyl groups as functional groups and the curing agent is a compound which is able to react with hydroxyl groups.
Preferred compositions are those in which the solubility parameter determined by the formula of K.W. Suh and J.M. Corbett (J. Appl. Pol. Sci. 12 (1968), 2359) of component (b) as well as of component (c) is greater than that of component (a) by at least 0.5.
Copolymer (a) contains either an organofluorine component or an organosilicon component in copolymerised form.
When it contains an organofluorine component, copolymer (a) preferably comprises (at) a polyfluoroolefin, (a2) at least one alkyl- and/or cycloalkylvinyl ether, (a3) a hydroxyalkylvinyl ether, (a4) an ethylenically unsaturated derivative of a UV absorber selected from the class of the 2-(2-hydroxyphenyl)benzotriazoles, of the o-hydroxyphenyl-s-triazines, of the o-hydroxybenzophenones or of the oxalanilides, and (as) further optional copolymerisable compounds.
Exemplary of polyfluoroolefins are l,l-difluoroethylene, tetrafluoroethylene or hexafluoropropylt,ne, but preferably chlorotrifluoxoethylene. Preferably the copolymer (a) contains at least 30 % of chlorotrifluoroethylene. , Alkylvinyl ethers are typically methylvinyl ether, ethylvinyl ether, propylvinyl ether, isopropylvinyl ether, butylvinyl ether, hexylvinyl ether or octylvinyl ether.
An illustrative example of cycloalkylvinyl ether is cyclohexylvinyl ether.
Illustrative examples of hydroxyalkylvinyl ethers are 2-hydxoxypropylvinyl ether, 3-hydroxybutylvinyl ether or 4-hydroxypentylvinyl ether.
Illustrative examples of copolymerisable derivatives of 2-(2-hydroxyphenyl)benzotriazoles are the compounds of the following formulae:

R3 r /N\
N
N~. R1 (CH2) X CO-X-A-O-CO-~=CH2 HO Rz R~ / % \
N
\N~ ~ 1 (CH2~-O-CO-C=CHZ

R3 ~ /N\
N
\N~ i H3 ~ 1 C - (CH2~-CO-X-A-O-CO-C=CH2 ;1 HO I ~ (CH2)g-CO-X-A-O-CO-C=CH2 R3 / / \ ~ CH3 N/

RI
HO CH2NHCOC=CH2 N
\ . wN/.

OT
HO

OCH2CHCH2-O-CO- ~ =CHi ~N~
wherein x is 0-3, Rl is H or CH3, R2 is H, Cl, Cl-C$alkyl, C3-C$alkenyl or C3-C~aralkyl, R3 is H, Cl, Cl-C4alkyl or Cl-C4alkaxy, X is -O- or -NH- and t~ is C2-CBalkylene, 2-hydroxytrimethylene or cyclohexylene.
Examples thereof are the compounds of the following formulae:
HO t-C4Hg ~N~
\ ~.N/
CH2CH2COOCH2CH20COCH=CH2 HO t-C4H9 i \N ~ ~

\ N/ I
CH2CH2COOCH2CH(OH~H20COC=CH2 HO t-C4H9 / .i \
N
o \N/
CH2CH2C0 O OCOCH=CH2 HO
OH CHg / ~N\
/N OCH2CHCH20COC=CH2 ~N~
HO t-C4H9 / iN\N
°N/
CH2CH2C0----O OCOC(CH3~CH2 HO t-C~H9 / i\
w wN/
CHZCH2COOCHZCH(CHg)OCOCH=CH2 HO t-C4H9 ~N~
\N/
CH2CH2-CONHCH~CH20COCH=CH2 HO ~_C4H9 ~N /
~N'~
~CH2CH2COOCH2CH(OH~H20COCH=CH2 Illustxative examples of copolymerisable derivatives of o-hydroxyphenyl-s-triazines are the compounds of formula I I
O ~B-O P CO-C=CH2 O CHa(CH2)COO- B-OCO- C=CH2 P
H Or ~ OH
N ~N N \N
Ar N EST Ar N
wherein p is 0 or l, RI is H or CH3, Ar is phenyl or phenyl which is substituted by Ct-C4alkyl and/or Cl, and B is C~-CBalkylene, cyclohexyl~ne or -CH2CH(OH)CH2-.
Exemplary of such compounds are:
2,4-diphenyl-6-(2-hydroxy-4-acryloyloxyethoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-5-(2-hydxoxy-4-acryloyloxyethoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-[2-hydroxy-3-methacryloyloxy-propoxy)phenyl)-s-triazine, 2,4-bis(2,4-dirnethylphenyl)-6-(2-hydroxy-4-methacryloyloxyphenyl)-s-triazine.
Exemplary of copolymerisable o-hydroxybenzophenones are the compounds of formula ~~~~'r~fl HO R

R ~ O
' ~ C O -- f B-O p CO-C=CH2 wherein p is 0 or 1, B is C2-C$alkylene, cyclohexylene or -CH2CH(OH)CH2-, Rl is H or CH3, and R4 and R5 are each independently of the other H, Cl-C4alkyl, ~OI-I or C1-C~alkoxy.
Exemplary of such compounds are:
2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, ' 2-hydroxy-4-(2-acryloyloxypropoxy)benzophenone, 2-hydroxy-4-(2-hydroxy-3-acryloyloxypropoxy)benzophenone, 2,2'-dihydroxy-4-(2-methacryloyloxyethoxy)benzophenone, 2-hydroxY-4-(2-acryloyloxyethoxy)benzophenone.
Illustrative examples of copolymerisable oxalamides are compounds of formula R7 ~ HN-CO-CO-NH ~ R6 Rt Rg O--°°f B-O p CO- C= CH2 ..
wherein p is 0 or 1, B is CZ-C$alkylene or -CH2CH(OH)CH2-, Rl is H or CH3, and Rs, R~
and R8 are each independently of one another H, Cl-Ct2alkyl or Ct-Ct2alkoxy.
Examplary of such compounds are:
N-phenyl-N'-(2-acryloyloxyphenyl)oxalarnide, N-p-tolyl-N'-(2-acryloyloxyphenyl)oxalamide, N-p-methoxyphenyl-N'-(2-acryloyloxyphenyl)oxalamide, N-p-methoxyphenyl-N'-[4-(2-acryloyloxyethoxy)phenyl]oxalarnide, N-p-methoxyphenyl-N'-[2-(2-methacryloyloxypropaxy)phenyl]oxalamide, N-phenyl-N'-[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]oxalarnide, N-p-methoxy-N'-[2-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]oxalamide, _g_ N-o-ethylphenyl-N'-[2-(2-acryloyloxyethoxy)phenyl]oxalamide.
Preferably componente (a4) is a derivative of 2-(2-hydroxyphenyl)benzotriazole or of o-hydroxyphenyl-s-triazine.
Exemplary of further copolymerisable compounds (component as) are styrene, «-methylstyrene, acrylic and methacrylic acid and the alkyl esters thereof, acrylonitrile, mono- or dialkyl maleates or maleimides. The copolymer may also contain as further copolymerisable compound (as) a copolymerisable sterically hindered amine.
Illustrative examples of suitable sterically hindered amines are 2,2,6,6-tetramethylpiperidine-4-(meth)acrylate or and 1,2,2,6,6-pentamethylpiperidine-4-(meth)acrylate.
Component (al) is preferably chlorotrifluoroethylene and is preferably present in copolymer (a) in an amount of at least 30 % by weight.
Preferably the fluorine-containing copolymer comprises 30-60 % by weight of component (al), 20-50 % of component (a2), 5-20 % of component (a3), 0.5-10 % of component (a~) and 0-15 % of component (as).
If the copolymer (a) contains a silicon-containing component, then (a) is preferably a copolymer of (al) an ethylenically unsaturated organosilicon compound, (a2) at least one alkyl acrylate or alkyl methacrylate, (a3) a hydroxyalkyl (meth)acrylate, (a4) an ethylenically unsaturated derivative of a iJV absorber selected from the class of the 2-(2-hydroxyphenyl)benzotriazoles, of the o-hydroxyphenyl-s-triazines, of the o-hydroxybenzophenones or of the oxalanilides, and (as) further optional copolymerisable compounds.
Exemplary of ethylenically unsaturated organosilicon compounds are vinylsilicon compounds, allylsilicon compounds or silicon-containing (meth)acrylates. As component (al) it is preferred to use a compound of formula ~~e?~~f~~
_g-(Y)n CHi-C C- O-(- CH2 )3 --- Si (Z)3-n w or ) CHa=--C-C- O--~ CH2 )g ° Si ~ O-Si (Y)n (Z) g-n~
3-m wherein n is 0-3, m is 0-3, R is H or CH3, Y is Ct-Cxalkyl and Z Ct-CBalkoxy or -OCH2CH20CH3. Exemplary of such compounds are:
1-[dimethyl-(3-acryloyloxypropyl)]-3-trimethyldisiloxane, 1-[dimethyl-(3-methacryloyloxypropyl)]-3-trimethyldisiloxane, 3-methacryloyloxypropyl-3-trimethoxysilane, 3-methacryloyloxypropyl-tris (trimethylsiloxy)silane.
The alkyl (methacrylates) used as component (a2) preferably contain an alkyl radical of 1 to 12; more particularly 1 to S, carbon atoms. Illustrative of such compounds are methyl (rneth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate or dodecyl (meth)acrylate.
The hydroxyalkyl (meth)acrylates used as component (a3) preferably contain a hydroxyalkyl radical of 2 to 6 carbon atoms. Illustrative of such compounds are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate or 2-hydroxyhexyl (meth)acrylate As UV absorber component (a4) it is possible to use the same compounds as for the fluorine-containing compounds cited hereinbefore. Here too the derivatives of 2-(2-hydroxyphenyl)benzotriazole and of o-hydroxyphenyl-s-triazine are preferred.

s.7 !" p ~;~.;:.~ ..n As further copolymerisable compounds (component as) it is possible to use typically styrene, «-methylstyrene, acrylic acid, methacrylic acid, acrylonitrile ar esters of malefic acid. The copolymer also may contain as further copolymerisable compound (as) a copolymerisable sterically hindered amine. Illustrative examples of suitable sterically hindered amines are 2,2,6,6-tetramethylpiperidine-4-(meth)acrylate and 1,2,2,6;6-pentamethylpiperidine-4-(meth)acrylate.
The silicon-containing copolymer (a) will preferably comprise 5-40 % of component (al), 30-70 % of component (a2), 5-20 % of component (a3), 0.5-10 % of component (a4) and 0-30 % of component {a$).
Component (b) is a (meth)acrylic copolymer customarily used as binder for coating compositions. These copolymers are also called acrylic resins. They consist mainly of one or more alkyl acrylates or alkyl methacrylates and contain a minor amount of a functional aerylate or methacrylate. The (meth)acrylic polymer thus contains functional groups which are able to react, with crosslinking, with a suitable curing agent.
A great number of such acrylic resins are commercially available. It is preferred to use an acrylic resin which is a copolymer of several alkyl acrylates or alkyl methacrylates, a hydroxyalkyl (meth)acrylate and acrylic or methacrylic acid.
Component (c) is a curing agent which is able to react with the functional groups of components (a) and (b), It is preferred to use as curing agent a melamine resin or a polyisocyanate or a mixture of both.
The melamine resins suitable for use as curing agents are preferably N-hydroxymethyl and N-alkoxymethyl derivatives of melamine. Such melamine derivatives suitable for use as curing agents are commercially available and are conventionally used for curing acrylic resins.
Suitable polyisocyanate curing agents are preferably diisocyanates and triisocyanates such as toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate, and the dimerised, trimerised or capped derivatives thereof.
The ratio of (a) to (b) may vary within a wide range. Preferably the weight ratio of {a):{b) is 20:80 to 80:20. The amount of curing agent (c) depends on the number of functional groups in (a) and (b). It is preferred to use 3 to 80 parts by weight of curing agent per 100 parts of (a) and (b). In a preferred embodiment of the invention, the novel mixture comprises 30-50 % by weight of (a), 30-50 % by weight of (b) and 10-25 ~'/o by weight of (c).
The novel compositions can be used as binders for weather- resistant coating compositions. In the simplest case, the coating compositions contain a mixture of the invention and a solvent. The coating compositions may be clear or pigmented compositions. Suitable pigments may be inorganic, organic or metallic pigments. The viscosity of the coating compositions can be regulated by adding solvents or thickeners.
The coating compositions may contain further modifiers such as fillers, plasticisers, levelling agents, adhesion promoters, accelerators, antioxidants or light stabilisers. The addition of light stabilisers selected from the class of the sterically hindered amines is of particular importance, as, together with the incorporated UV absorber of the binder, these compounds are able to effect a synergistic enhancement of weatherability.
Illustrative examples of preferred sterically hindered amines are the derivatives of 2,2,6,6-tetramethylpiperidine described in Kunststoffe 77 (1987) 1065-69 or in EP-A-156 52 on pages 5-17.
Depending on the curing agent used, these coating compositions can be cured at room temperature or at elevated temperature. In each case, curing is accelerated by heating (stoving). Acceleration can also be effected by adding curing catalysts. Thus, for example, curing with isocyanates can be accelerated by organotin compounds or by basic catalysts (for example tertiary amines). Curing with melamine resins can be accelerated by acid catalysts, for example by addition of toluenesulfonic acid.
The cured coating compositions are distinguished not only by excellent weathering resistance, but also by high gloss. Suitable substrates can be the customary ones, such as metal, wood, ceramic materials or plastics materials. If multilayer coats are applied, the coating compositions containing the binders of this invention are preferably used as topcoats, as they screen against UV radiation. The invention likewise relates to the cured finishes obtained with the novel coating compositions.
The following Examples illustrate the invention in detail. Parts and percentages are by weight.

s J

Examples Example 1: Preparation of a fluorine-containing copol In a 400 ml autoclave fitted with stirrer, 25.24 g of cyclohexylvinyl ether, 14.42 g of ethylvinyl ether, 11.61 g of hydroxybutylvinyl ether and 5.73 g of UV absorber HO t-C4H9 / ~ ~ ~ ~ UV-1 O CI-Ig II i CH2CH2COOCH2CH(OH~H20-- C' C=CH2 are dissolved, under nitrogen, in 1 i0 g of tert-butanol, and 2 g of KZC03 and 0.1 g of azoisobutyronitrile are added. To remove released air, the solution is solidified by cooling with liquid nitrogen. After warming to roam temperature, 58.24 g of chlorotrifluoro-ethylene are added, the autoclave is closed and heated slowly, with stirring, to 65°C. This temperature is kept for 7 hours and then cooled to room temperature. The solid copolymer is precipitated by pouring the resultant solution into water. It is washed with water and dried. The limiting viscosity [,~] of the copolymer is 0.30 dl/g. Elemental analysis shows that the copolymer contains 5 % of UV absorber.
Example 2: Example 1 is repeated, using as UV absorber 5.73 g of the compound HO t-C4H9 ~ ~ / ~ uV-2 N
~CH2CH2C00 O-CO-CH=CH2 The copolymer obtained contains 5 % of UV absorber.
Example 3: Example 1 is repeated, using as UV absorber 5.73 g of the compound r.J ~ J

OCH2CH(OH~H20--- CL- C=CH2 'OH

CH3 N ~ N CH3 N/
r i CHg CHg The copolymer obtained contains 5 % of UV absorber.
Example 4: Example 1 is repeated, using as UV absorber 5.73 g of the compound HO
O O
C ~ ~ OCH2GH2O-C--CH=CH2 UV-4 The copolymer obtained contains 5 % of UV absorber.
Example 5~ Example 1 is repeated, using as UV absorber 5.73 g of the compound O
~I

O
NH-C-C-NH ~

The copolymer obtained contains 5 % of UV absorber.

Example 6: Preparation of a silicon-containing copolymer A mixture of 90 g of xylene and 10 g of 4-methyl-2-pentanone is heated to 105°C. At this temperature, a mixture of 10 g of 3-methacryloyloxypropylpentamethyl disiloxane, 16.9 g of styrene, 7.3 g of methyl methacrylate, 46.5 g of 2-ethylhexyl methacrylate, 16.2 g of 2-hydroxyethyl methacrylate, 3.1 g of methacrylic acid, 5.2 g of UV absorber UV-1 and 0.7 g of azoisobutyronitrile is added dropwise over 4 hours. The mixture is then stirred for 2 hours at the same temperature, to give a ca. 50 % solution of the copolymer.
The copolymer contains 5 % of UV absorber in copolymerised form.
Example 7: Example 6 is repeated, using 5.2 g of compound UV-3 as UV absorber.
The copolymer obtained contains S % of UV absorber.
Example 8: Example 6 is repeated, using 5.2 g of compound UV-4 as UV absorber.
The copolymer obtained contains 5 % of UV absorber.
Example 9: Example 6 is repeated, using 5.2 g of compound UV-5 as UV absorber.
The copolymer obtained contains 5 % of UV absorber.
Example 10: Prev~aration of clear coating compositions with melamine curing agent Mixtures are prepared from 19.5 parts of a copolymer which contains fluorine and UV absorber (product of Example 1), 19.5 parts of an acrylic resin (copolymer of 31 % of ethyl acrylate, 29.5 % of methyl methacrylate, 20.2 % of 2-ethylhexyl methacrylate, 16.2 % of 2-hydroxyethyl methacrylate and 3.1 % of methacrylic acid, and 9.8 parts of a melamine resin (Cymel~ 1130, Cyanamid Corp.) as curing agent. The mixtures contain ca. 2 % of UV absorber, based on solids. They are then diluted with xylene to sprayable consistency and applied to aluminium sheets coated with a silver metallic primer lacquer.
The test pieces are stored for 1S minutes at room temperature and then stoved for 30 minutes at 130°C. The finish so obtained has a film thickness of 40-45 wm.
A clear coating composition the fluorine-containing copolymer of which was prepared as described in Example 1, but without UV absorber, as well as the same formulation to which 2 % (based on solids) of UV-1 has been added, is used for comparison purposes.
The formulation of the coating composition and the coating of the test pieces are as described above.
The cured test pieces are subjected to accelerated weathering in a UVCON~

Weather-O-Meter (with UVB-313 lamps) and in a xenon Weather-O-Meter {CAM 159, KFA method). The 60° gloss according to DIN 67 530 is measured as the criterion for assessing damage.
Table 1- UVCON Weathering (8 h exposure at 70°C/4 h condensation at 50°C) 60° gloss (in%) after Stabiliser 0 400 1200 1600 h without 87 40 15 -2 % of UV-1 incorporated 94 84 54 37 (copolymer of Ex, 1) 2 % of UV-1 added 87 64 25 20 Table 2 - Xenon Weather-O-Meter Stabiliser 60° gloss (%) after 800 h without 18 2 % of UV-1 incorporated 49 (copolymer of Ex. 1) 2 % of UV-1 added 18 Example 11: Example 10 is repeated, using 19.5 parts of the copolymer of Example 3 in place of the copolymer of Example 1. The clear coating composition contains ca. 2 % of UV-3, based on solids.
The test pieces are coated as described in Example 10 and tested in a CAM 159 xenon Weather-O-Meter and by measuring the 60° gloss in accordance with DIN
67 530.

Table 3 - Xenon Weather-O-Meter Stabiliser 60° gloss (%) after 800 h without 18 2 % of UV-3 incorporated 42 (copolymer of Ex. 3) 2 % of UV-3 added 19 Example 12: Mixtures are prepared from 19.5 parts of the silicon-containing copolymer of Example 6, 19.5 parts of the acrylic resin used in Example 10; and 9.8 parts of melamine resin (Cymel~1130) as curing agent. The mixtures contain ca. 2 % of UV
absorber, based on solids.
A mixture prepared by using a silicon-containing copolymer which does not contain UV
absorber as comonomer, but which has otherwise been prepared as described in Example 6, is used for comparison purposes.
The test pieces are coated and tested as described In Example 10. The results are reported in Table 4.
Table 4 - Weathering in a xenon Weather-O-Meter Stabiliser 60° gloss (%) after 2000 h without 40 2 % of UV-1 incorporated 52 (copolymer of Ex. 6) 2 % of UV-3 incorporated 60 (copolymer of Ex. 7) Example 13' Clear coating composition with isocyanate curing went Mixtures are prepared from 19.5 parts of the fluorine-containing copolymer of Examples 1 and 3, 19.5 parts of the acrylic resin described in Example 10, and 5.2 parts of an alipharic ~~~~~~~~f~

triisocyanate (Desmodur~ N 75, Bayer A.G.). The mixtures contain ca. 2.2 % of UV
absorber, based on solids.
The mixtures are diluted with xylene to sprayable consistency and applied to aluminium sheets coated with a silver metallic primer lacquer. The test pieces are air-dried for 15 minutes at room temperature and then cured for 45 minutes at 80°C. The finish so obtained has a film thickness of 40-45 wm.
A coating composition the fluorine-containing copolymer of which has been prepared as described in Example 1, but without UV absorber as cornonomer, is used for comparison purposes. Further, to this formulation is added once 2.2 % of UV-1 and once 2.2 % of UV-3. The results obtained after subjecting the test pieces to weathering for 1200 hours in the UVCON Weather-O-Meter (8 h exposure at 70°C, 4 h condensation at 50°C) are reported in Table 5.
Table 5 - Weathering in UVCON Weather-O-Meter Stabiliser 60° gloss (%) after 1200 h without 9 2 % of UV-1 incorporated 78 (copolymer of Ex. 1) 2 % of UV-1 added 46 2 % of UV-3 incorporated 63 (copolymer of Ex. 3) 2 % of UV-3 added 16 Example 14: A mixture is prepared from 19.5 parts of the silicon-containing copolymer of Example 7, 19.5 parts of the acrylic resin used in Example 10, and 5.2 parts of Desmodur~ N75. The mixture contains ca. 2.2 % of UV-3 in copolymerised form.
In the same manner, a mixture is prepared whose silicon-containing copolymer has been prepared as described in Example 7, but without UV absorber as comonomer. This mixture is used once without and once with addition of 2.2 % of UV-3 (based on solids).

~~~5~~
- is -The coating of the test pieces and testing in the UVCON Weather-O-Meter ($h exposure at 70°C, 4 h condensation at 50°C) are as described in Example 10. The results are reported in Table 6.
Table 6 - Weathering in UVCON Weather-O-Meter Stabiliser 60° gloss (%) after 2000 h without 22 (cracking) 2 % of UV-3 incozporated 47 (copolymer of Ex. 7) 2 % of UV-3 added 24

Claims (21)

1. ~A curable composition comprising (a) a fluorine-or silicon-containing copolymer, (b) a (meth)acrylic copolymer, and (c) at least one curing agent, each of which two said copolymers contains functional groups which are able to react with the curing agent, wherein component (a) contains a UV absorber in copolymerised form.
2. The composition according to claim 1, wherein the copolymers (a) and (b) contain hydroxyl groups and the curing agent is a compound which is able to react with hydroxyl groups.
3. The composition according to claim 1 or 2, wherein component (a) is a fluorine-containing copolymer.
4. The composition according to claim 1, wherein component (a) is a copolymer comprising:
(a1) an olefin containing more than one fluorine atom, (a2) at least one of an alkylvinyl ether and a cycloalkylvinyl ether, (a3) a hydroxyalkylvinyl ether, and (a4) an ethylenically unsaturated derivative of a UV
absorber selected from the class of the 2-(2-hydroxyphenyl)-benzotriazoles, of the o-hydroxyphenyl-s-triazines, of the o-hydroxybenzophenones or of the oxalanilides.
5. The composition according to claim 4, wherein component (a) additionally comprises:
(a5) further copolymerisable compounds selected from styrene, .alpha.-methylstyrene, acrylic acid, methacrylic acid, -20-~

and the alkyl esters thereof, mono- or dialkyl maleates, and mono- or dialkyl maleimides.
6. ~The composition according to claim 4 or 5, wherein component (a1) is chlorotrifluoroethylene and is present in the copolymer (a) in an amount of at least 30% by weight.
7. ~The composition according to any one of claims 4 to 6, wherein component (a4) is a derivative of 2-(2-hydroxyphenyl)-benzotriazole or of o-hydroxyphenyl-s-triazine.
8. ~The composition according to claim 1, wherein component (a) is a silicon-containing copolymer.
9. ~The composition according to claim 1, wherein component (a) is a copolymer of (a1) an ethylenically unsaturated organosilicon compound, (a2) at least one alkyl acrylate or alkyl methacrylate, (a3) a hydroxyalkyl (meth)acrylate, and (a4) an ethylenically unsaturated derivative of a UV-absorber selected from the class of the 2-(2-hydroxyphenyl)-benzotriazoles, of the o-hydroxyphenyl-s-triazines, of the o-hydroxybenzophenones or of the oxalanilides.
10. ~The composition according to claim 9, wherein component (a) additionally comprises:
(a5) further copolymerisable compounds, selected from styrene, .alpha.-methylstyrene, acrylic acid, methacrylic acid, and the alkyl esters thereof, mono- or dialkyl maleates, and mono- or dialkyl maleimides.
11. ~The composition according to claim 9 or 10, wherein component (a1) is a compound of formula wherein n is 0-3, m is 0-3, R is H or CH3, Y is C1-C8alkyl and Z is C1-C8alkoxy or -OCH2CH2OCH3.
12. The composition according to any one of claims 9 to 11, wherein component (a4) is a derivative of 2-(2-hydroxyphenyl)-benzotriazole or of o-hydroxyphenyl-s-triazine.
13. The composition according to any one of claims 1 to 12, wherein component (b) is a copolymer of several alkyl acrylates or alkyl methacrylates, a hydroxyalkyl (meth)acrylate and acrylic or methacrylic acid.
14. The composition according to any one of claims 1 to 13, wherein component (c) is at least one of a melamine resin and a polyisocyanate.
15. The composition according to any one of claims 1 to 14, wherein the weight ratio of (a) to (b) is 20:80 to 80:20, and the weight ratio of (c) to the sum of (a) and (b) is 3-80 to 100.
16. ~The composition according to claim 1, wherein the copolymer (a) contains a copolymerisable sterically hindered amine.
17. ~Use of the composition according to any one of claims 1 to 16, as binder for clear or pigmented coating compositions.
18. ~A clear or pigmented coating composition which contains as binder the composition according to any one of claims 1 to 16.
19. ~The clear or pigmented coating composition according to claim 18, which contains a light stabiliser selected from the class of the sterically hindered amines.
20. The clear or pigmented coating composition according to claim 19, which contains a derivative of 2,2,6,6-tetramethylpiperidine.
21. A cured film obtained by curing a coating composition which contains as binder the composition according to any one of claims 1 to 16.
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JP3157231B2 (en) * 1991-12-12 2001-04-16 三菱化学株式会社 Water-crosslinkable polyolefin pipe with excellent weather resistance
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JPH0952916A (en) * 1995-08-11 1997-02-25 Asahi Denka Kogyo Kk Ultraviolet light absorbing composition
US5985463A (en) * 1998-06-24 1999-11-16 E.I. Du Pont De Nemours And Company Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance
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