Classifications

• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

• the invention relates to coating compositions made from mixtures of polymerizable compounds, aminoplast resins and catalysts which trigger a free-radically initiated polymerization at temperatures above about 60 ° C. and are converted into acids.
• DE-OS 1 919 678 discloses photoinitiators which contain one or more acidic groups which disintegrate under the action of UV light and release an acid.
• the ⁇ -methylol-benzoin (ether) sulfonic acid esters described therein are amino resins, Phenol formaldehyde resins or other acid curable resins are added and the mixture cured by UV light. There is no indication in the literature cited of a polymerization initiated thermally by means of these catalysts.
• photopolymerizable coating mixtures From DE-OS 2 610 437 photopolymerizable coating mixtures are known, the photopolymerizable monomers with ester groups, a polymer containing carboxyl groups, an aminoplast resin and mixtures of photo initiacoren can contain. Here too, reference is made exclusively to a photopolymerization process for curing coatings.
• photopolymerizable mixtures for producing molding compositions consist of mixtures of an unsaturated polyester, at least one hydroxyl group, olefinically unsaturated, photopolymerizable monomers, a melamine compound containing methylol groups, an inhibitor and a photoinitiator.
• the mixture is cured by photopolymerization and simultaneous or subsequent addition of heat. Hot curing is accelerated by adding p-toluenesulfonic acid.
• a disadvantage of such mixtures is the insufficient storage stability, which is particularly effective when the mixtures described are used as coating agents.
• a further serious disadvantage of the coating compositions curable by means of photopolymerization is that they can only be pigmented to a limited extent.
• the object was achieved in that polymerizable mixtures of at least one polymerizable monomer and at least one aminoplast are cured in the presence of special catalysts, the catalyst triggering a free-radically initiated polymerization at temperatures above 60.degree. C. and converting into acids, which in turn cause the polycondensation reactions of Catalyze aminoplast resins with reactive groups (OH, NH).
• the invention thus relates to heat-polymerizable coating compositions which may contain solvents, dyes, pigments and other customary paint auxiliaries, from mixtures of characterized in that the catalyst, which contains one or more sulfonic acid ester groups, triggers a free-radically initiated polymerization at temperatures above 60 ° C and forms acids upon decomposition which in turn catalyze polycondensation of aminoplast resins with reactive groups.
• the catalyst which contains one or more sulfonic acid ester groups, triggers a free-radically initiated polymerization at temperatures above 60 ° C and forms acids upon decomposition which in turn catalyze polycondensation of aminoplast resins with reactive groups.
• the mixtures preferably consist of 80-97% by weight of component A) and 3-20% by weight of component B, the sum of the percentages by weight of A) and B) being 100 and the catalyst in an amount of 0, 1 - 10 wt .-%, based on the sum of A) and B), is contained in the mixture.
• the unsaturated polyester resins up to 50 mol% of the unsaturated condensed dicarboxylic acids can be replaced by other dicarboxylic acid units such as phthalic acid, isophthalic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, succinic acid, adipic acid.
• dicarboxylic acid units such as phthalic acid, isophthalic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, succinic acid, adipic acid.
• the carbon chains of the glycols, polyether glycols, polyols or polyether polyols can be interrupted by 1 or more nitrogen atoms.
• polyepoxypolyacrylates i.e. H. Reaction products of polyepoxides and an ethylenically unsaturated monocarboxylic acid such as (meth) acrylic acid, 60 to 100%, preferably 100%, of the epoxy groups having been converted.
• polyepoxides are understood to mean compounds which contain more than one 1,2-epoxy group per molecule, preferably 2 to 6, in particular 2, epoxy groups.
• Polyglycidyi- ethers of polyhydric phenols can be, for example, pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane of from 4,4'-D ihydroxy-3,3'-dimethyldiphenylmethane 4,4'-dihydroxydiphenyldimethylmethane from (Bisphenol A), from 4,4'-dihydroxydiphenylmethylmethane, from 4,4'-dihydroxydiphenylcyclohexane, from 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, from 4,4'-dihydroxydiphenyl, from 4.4 '-Dihydroxydiphenylsulfon, from tris- (4-hydroxyphenyl) -methane, from the chlorination and bromination products of the above diphenols, in particular from bisphenol A; from novolaks (ie from reaction
• Glycidyl ethers of polyhydric alcohols for example from 1,4-butanediol, 1,4-butenediol, glycerol, trimethylolpropane, pentaerythritol and polyethylene glycols, may also be mentioned.
• triglycidyl isocyanurate N, N'-D iepoxypropyloxyamid
• Polyglycidylthio expediher of polyhydric thiols such as from Bismercaptomethylbenzol, diglycidyl trimethylentrisulfon, epoxidized polybutadiene, epoxidized linseed oil, vinylcyclohexene diepoxide.
• Glycidyl esters of polyvalent aromatic, aliphatic and cycloaliphatic carboxylic acids for example, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl adidate and methyl ester of hexahydrophthalate, and 2 moles of a diol or 1 / n mole of a polyol with n hydroxyl groups, such as glycidyl carboxylic acid esters of the general formula in which A is an at least divalent radical of an aliphatic hydrocarbon which may be interrupted by oxygen and / or cycloaliphatic rings or the divalent radical of a cycloaliphatic hydrocarbon, R is hydrogen or alkyl radicals having 1-3 C atoms and n is a number between 2 to 6 mean, or mixtures of glycidyl carboxylic acid esters of the indicated general formula (see British Patent 1,220,702).
• Preferred polyepoxide compounds are polyglycidyl ether of bisphenol A and polyglycidyl ester of hexahydrophthalic acid, which have optionally been pre-extended with a dicarboxylic acid, for example adipic acid, succinic acid, isophthalic acid or maleic acid or with ammonia, amines or H 2 S, dithiols or polxthiols.
• a dicarboxylic acid for example adipic acid, succinic acid, isophthalic acid or maleic acid or with ammonia, amines or H 2 S, dithiols or polxthiols.
• the advance can be carried out with 0.01 to 0.5 NH equivalents, based on epoxy equivalent, of ammonia or an aliphatic or cycloaliphatic primary or secondary amine or a mixture of the aforementioned nitrogen compounds.
• dicarboxylic acids tri- and polyfunctional polycarboxylic acids may also be possible. are used, the amount also varies between 0.01 and 0.6 carboxyl equivalents per 1 epoxy equivalent.
• This pre-extension can be carried out by simply reacting at room temperature or elevated temperature in the case of ammonia, the amines and SH compounds or at elevated temperature in the case of the carboxylic acid.
• the pre-extended epoxy compounds always represent polyepoxides with more than one 1,2-epoxy group and are known from the literature.
• reaction with the nitrogenous component takes place at 20-90 ° C and with the (meth) acrylic acid or the carboxylic acids c) at 40-90 ° C, each in bulk or inert organic solvents; where in the case of com Components b) and c) also 0.01-3% by weight, based on the starting epoxide, of catalysts such as tertiary amines, alkali metal salts of organic carboxylic acids, alkali metal hydroxides, phosphines, arsines or stibines can be added.
• catalysts such as tertiary amines, alkali metal salts of organic carboxylic acids, alkali metal hydroxides, phosphines, arsines or stibines can be added.
• the listed polymerizable monomers A) of groups I to XI can be mixed with one another in any desired ratio, for example monomers of group IX with monomers of groups I to IV or monomers of III with those of groups I, II and IV. However, preference is given to the polyepoxypolyacrylates of group XI alone or in combination with monomers of at least one of groups I to IV and VIII.
• aminoplast resins B) used are: urea aldehyde resins, such as are obtained in a known manner by condensation of urea or urate derivatives and aldehydes such as formaldehyde, acetaldehyde, etc., preferably in the presence of C 1 -C 6 monoalcohols.
• Aminotriazinaldehyde resins which are known in a known manner by condensation of aminotriazines, in particular melamine, with an aldehyde such as formaldehyde, acetaldehyde, benzaldehyde and the like, in particular formaldehyde preferably in the presence of a lower alcohol such as methanol, ethanol, propanol or butanol.
• aldehyde such as formaldehyde, acetaldehyde, benzaldehyde and the like
• formaldehyde preferably in the presence of a lower alcohol such as methanol, ethanol, propanol or butanol.
• a lower alcohol such as methanol, ethanol, propanol or butanol.
• Such products are also commercially available, for example hexamethoxymethylmelamine.
• ⁇ -hydroxymethylbenzoin-methanesulfonic acid ester ⁇ -benzenesulfonalure ester, -p-toluenesulfonic acid ester and -B-naphthalenesulfonic acid ester
• the ⁇ -hydrcixymethyl-4,4'-dimethylbenzoin-benzeneaulfonic acid ester the ⁇ -hydroxymethyl-4,4'- dichlorobenzoin-benzenesulfonic acid ester
• the ⁇ -hydroxymethylbenzoin-isopropyl ether-benzenesulfonic acid ester and the bis- ( ⁇ -hydroxymethylbenzoin) -diphenylmethane-4,4'-disulfonate.
• the mixture with inert solvents such as butyl acetate, ethyl acetate, ethanol, isopropanol, butanol, acetone, ethyl methyl ketone, diethyl ketone, cyclohexane, cyclohexanone is, of course, to set a desired viscosity , Cyclopentane, cyclopentanone, n-heptane, n-hexane, n-octane, isooctane, toluene, xylene, methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride.
• inert solvents such as butyl acetate, ethyl acetate, ethanol, isopropanol, butanol, acetone, ethyl
• the usual fillers and pigments can also be used, such as talc, heavy spar, chalk, gypsum, silicas, asbestos flours, light spar, Ti0 2 and colored pigments.
• the coating agents can be applied to suitable substrates by means of methods customary in the paint industry, such as spraying, rolling, knife coating, printing, dipping, flooding, brushing, brushing.
• Suitable substrates are paper, cardboard, leather, wood, plastics, textiles, ceramic materials, metals, preferably paper and cardboard, and wood and metal.
• a mixture is made from the following ingredients:
• Example 2 After a baking time of 10 minutes at 160 ° C, coatings are obtained which are sticky on the surface.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)

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Citations (1)

• 1977
  • 1977-07-02 DE DE19772730098 patent/DE2730098A1/de active Pending
• 1978
  • 1978-06-26 EP EP78100238A patent/EP0000193A1/fr not_active Withdrawn
  • 1978-06-30 JP JP7881578A patent/JPS5414434A/ja active Pending
  • 1978-06-30 IT IT7850120A patent/IT7850120A0/it unknown

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