Powder coating composition

FIELD: polymer coatings.

SUBSTANCE: invention relates to using powder composition to coat jet printing materials utilized as visual information carriers. Powder composition contains (i) one or several powder silane-containing polyvinyl alcohols based on copolymers of fully or partially hydrolyzed esters having degree of hydrolysis from 75 to 100 mol % and (ii) one or several water re-dispersible polymer powders based on homopolymers or copolymers of one or several monomers selected from group including nonbranched or branched C1-C15-alkylcarboxylic acid vinyl esters, (meth)acrylic acid esters with C1-C15-alcohols, vinylaromatic compounds, olefins, dienes, and vinyl halides.

EFFECT: enabled manufacture of wear-resistant coatings to coat both paper and polymeric substrates, avoided undesired increase in viscosity during composition preparation procedure, and enabled more flexible variation in contents of solids in chalking mass.

10 cl, 15 ex

 

The present invention relates to a powder composition for coatings used as carriers of visual information materials for inkjet printing.

To make markings on the paper covering the best gloss and to improve the degree of whiteness in coating mass as an additional binder type polyvinyl alcohols. Applied to the paper coating, primarily on paper designed for inkjet printing, are subjected to high mechanical loads. Therefore, one of the main requirements for such coatings is their high resistance to abrasion. In addition, the coating composition should provide a good absorption of the ink without bleeding.

From the application DE-A 10232666 known that selectabase polyvinyl alcohols are highly effective binder for coating masses. In the application DE-A 3519575 as a means of coating to obtain a coating layer, designed for use on heat-sensitive paper, it is recommended to use a combination of the silane modified polyvinyl alcohol and colloidal silicic acid. In the application EP-A 1080940 describes water-resistant composition for coatings containing polyvinyl alcohol with a silanol functional group and a chelate compound of titanium.

Coz the ACLs JP-A 10-119430 for coating heat-sensitive materials-visual media is used an aqueous solution, containing modified by silane polyvinyl alcohol, a ternary copolymer of isobutylene, maleic anhydride and maleinimide, metal salt and a crosslinking agent. Application of the modified silane polyvinyl alcohol as a means of coating the paper also recommended in the patent US 4617239, which provides for the use of silanizing polyvinyl alcohol in aqueous alkaline solution, optionally in combination with latex. From EP-A 1127706 known material for inkjet printing, which is coated from a mixture of an aqueous solution silanizing polyvinyl alcohol, latex and dispersion of the corresponding pigment.

The disadvantage of such known from the prior art mixtures is unsatisfactory in many cases, stability of solutions of polyvinyl alcohols during storage. When using mixtures of solutions of polyvinyl alcohols and dispersions of the polymers to the desired final concentration is often impossible to achieve due to a substantial increase in the viscosity of the applied concentrated solutions, respectively dispersions.

Based on the foregoing, the present invention was based on the task to develop a composition for coating materials for inkjet printing, which would allow to obtain abrasion-resistant coatings for application on UMaine, and on a polymeric substrate (base) and to avoid undesirable increase in viscosity in the process of its production and which would provide a more flexible variation of the content of solids in coating weight.

The object of the invention in accordance with this is the application of the powder composition to be applied on materials for inkjet printing coating, which contains

a) one or more powder, selectarray polyvinyl alcohol-based fully or partially saponified copolymers of vinyl esters with a degree of hydrolysis of 75 to 100 mol.% and

b) one or more holder in water polymer powders based on homopolymers or copolymers of one or more monomers selected from the group comprising vinyl esters of unbranched and branched alkylcarboxylic acids with 1-15 carbon atoms, esters of methacrylic acid and esters of acrylic acid and alcohols with 1-15 carbon atoms, vinylaromatic compounds, olefins, diene and vinylchloride.

Selectabase polyvinyl alcohol-based fully or partially saponified copolymers of vinyl esters with a degree of hydrolysis of 75 to 100 mol.% can be obtained by radical polymerization of one or more vinyl esters of unbranched or branched, alkylarene what's acids with 1-15 carbon atoms and one or more selectarray, the ethylene unsaturated monomers, and optionally other copolymerizing with them comonomers and saponification thus obtained polymers.

Suitable for use in the above order selectabase polyvinyl alcohols are completely or partially saponified copolymers of vinyl esters with a degree of hydrolysis of 75 to 100 mol.% and with selectabase demonomanie links in an amount of from 0.01 to 10 mol.%. Completely saponified copolymers of vinyl esters have a degree of hydrolysis of preferably from a 97.5 to 100 mol.%, particularly preferably from 98 to 99.5 mol.%. The degree of hydrolysis of the partially saponified vinyl ester is preferably from 80 to 95 mol.%, particularly preferably from 86 to 90 mol.%. Viscosity is determined using a viscometer of Heppler 4%by weight aqueous solution according to DIN 53015, is a measure of molecular weight and degree of polymerization of partially or completely saponified silanizing of polymers of vinyl ester is preferably from 2 to 50 MPa·C.

Suitable for use as provided for by the invention of the order complex of vinyl esters are vinyl esters of unbranched or branched carboxylic acids with 1-15 carbon atoms. To the preferred vinyl esters are vinyl acetate, finalproject vinylboronate, vinyl-2-ethylhexanoate, vanillaware, vinylbilt and vinyl esters α-branched monocarboxylic acids 5-13 carbon atoms, for example the products VeoVa9®or VeoVa10®(trade name for product of Shell company). Most preferred among them vinyl acetate.

Suitable for use in these purposes the ethylene unsaturated selectabase monomers are among other ethylene unsaturated silicon compounds of General formula R1SiR20-2(OR)1-3where R1denotes CH2=CR4-(CH2)0-3or CH2=CR4CO2(CH2)1-3, R2represents C1-C3the alkyl residue With1-C3CNS residue or a halogen, preferably C1 or Br, R3represents an unbranched or branched, optionally substituted alkyl residue with 1 to 12, preferably 1 to 3 carbon atoms or acyl residue with 2 to 12 carbon atoms, R3optionally can be interrupted by ether group, and R4represents N or CH3.

It is suitable for use ethylene unsaturated selectabase the monomers are also containing silane groups, (meth)acrylamide General formula CH2=CR5-CO-NR6-R7-SiR8m-(R9)3-mwhere will oboznachaet 0-2, R5is either In, or methyl group, R6represents H or alkyl group with 1-5 carbon atoms, R7represents alkylenes group with 1-5 carbon atoms or a bivalent organic group in which the carbon chain is interrupted by O - or N-atom, R8represents an alkyl group with 1-5 carbon atoms, and R9is alkoxygroup from 1-40 carbon atoms, which may be substituted by other heterocycles. In the monomers, in which there are two or more R5or R9groups, these groups may be identical or different.

As examples of such (meth)acrylamidoglycolate can be called 3-(meth)acrylonitrilebutadiene, 3-(meth)acrylamidophenylboronic, 3-(meth)acrylamidoethyl(β-methoxyethoxy)silane, 2-(meth)acrylamide-2-methylpropionitrile, 2-(meth)acrylamide-2-methylethylketoxime, N-(2-(meth)acrylamidoethyl)aminopropyl-trimethoxysilane, 3-(meth)acrylamidophenylboronic, 2-(meth)acrylonitrilebutadiene, 1-(meth)acrylonitrilebutadiene, 3-(meth)acrylonitrilebutadienestyrene, 3-(meth)acrylamidoethyl-dimethylethoxysilane, 3-(N-methyl(meth)acrylamide)propyltrimethoxysilane, 3-((meth)acrylamidoethyl)-3-hydroxypropyltrimethylammonium, 3-((meth)acrylamidoethyl is)propyltrimethoxysilane, N,N-dimethyl-N-triethoxysilylpropyl-3-(meth)acrylamidophenylboronic and N,N-dimethyl-M-triethoxysilylpropyl-2-(meth)acrylamide-2-methylpropylamine.

For the preferred ethylene unsaturated selectabase the monomers are γ-acrylic-, respectively γ-methacryloxypropyl three(alkoxy)silanes, α-methacryloxyethyl(alkoxy)silanes, γ-methacryloxypropyl(alkoxy)silanes, vinylsilane, such as vinylamide(alkoxy)silanes and vinyltris(alkoxy)silanes, as alkoxygroup can be used, for example, remains ethers methoxy-, ethoxy, Meliksetyan, amoxicillin-methoxypropylamine, respectively ethoxypropylamine. Examples of preferred selectarray monomers are 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, VINYLTRIMETHOXYSILANE, wikimediamessages, vinyltriethoxysilane, vinylpyridinium, vinyltriethoxysilane, VINYLTRIMETHOXYSILANE, vinyltris(1-methoxy)isopropoxide, VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl(2 methoxyethoxy)silane, vinyltrichlorosilane, vinylpyridinium, vinyltris(2 methoxyethoxy)silane, triacetonediamine, allylisothiocyanate, allyltriethoxysilane, wine is dimethylethoxysilane, vinylimidazole, vinilimidazolii, vinylimidazoles, minimizebuttonmacstylename, vinyltriethoxysilane, VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, vanillachocolad, vinyltriethoxysilane, vinylidenechloride, fenilmetilketil, vanillateensblackcream, vinylidenechloride and modified polyethyleneglycol vinylsilane.

Most preferred as ethylene unsaturated selectarray monomers of VINYLTRIMETHOXYSILANE, wikimediamessages, vinyltriethoxysilane, vinylpyridinium, vinyltris(1-methoxy)isopropoxide, 3-methacryloxypropyl(2 methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylate-auxipropilmetilzelluloza and methacryloxypropyltrimethoxysilane, and mixtures thereof or a mixture of two or more silanes of the group, including 3-methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, VINYLTRIMETHOXYSILANE and vinyltriethoxysilane.

For copolymerization of ethylene unsaturated selectabase monomers are used in amounts of from 0.01 to 10.0 mol.%, preferably from 0.01 to 1.0 mol.%.

Along with selectabase monomers for copolymerization can be used with one or more other comonomers, selected is from the group includes 1-alkylvinyl esters, such as isopropenylacetate, ethylene, propylene, isobutylene, butadiene, isoprene, chloroprene, styrene, α-methylsterol, vinyl chloride, vinylidenechloride, viniferin, Acrylonitrile, Methacrylonitrile, simple alkylvinyl esters, such as ethylenically ether, n-butylvinyl ether, isobutylphenyl ether, tert-butylvinyl ether, cyclohexylaniline ether, octadecylsilyl ether, hydroxybutylidene ether and monomineralic ether cyclohexanedimethanol, vinylmation, N-vinylformamide, N-vinyl-N-methylacetamide, N-vinylcaprolactam, N-vinyl pyrrolidone and N-vinylimidazole.

Suitable for use are further acrylic acid and methacrylic acid and their esters and amides, such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, ethylhexyl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, n-hexyl(meth)acrylate, isooctyl(meth)acrylate, Isodecyl(meth)acrylate, lauryl(meth)acrylate, methoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, α-harakaly ether and α-cyanacrylate ether.

As other examples, vinylcarbazole, vinylidene, complex, vinyl esters, the anhydride acrylic acid, maleic anhydride is islote, esters of maleic and fumaric acid, modified sulfonic acid monomers such as 2-acrylamide-2-methylpropanesulfonic acid and its salts with alkali metals, cationic monomers, such as trimethyl-3-(1-(meth)acrylamide-1,1-dimethyl-propyl)ammoniacal, trimethyl-3-(1-(meth)acrylamidoethyl)ammoniacal, 1-vinyl-2-Mei and their Quaternary compounds.

Selectabase polymers of vinyl esters can be obtained in a known manner by polymerization, preferably by polymerization in mass, emulsion polymerization, suspension polymerization or polymerization in organic solvents, particularly preferably in an alcohol solution. The molecular weight can be adjusted in a known manner by polymerization in the presence of molecular weight regulators. Saponification selectarray polymers of vinyl esters is conducted according to known methods, for example in a reactor with a belt conveyor or kneading apparatus or in the apparatus with a stirrer, in alkaline or acid medium by adding acid or base. Upon completion of hydrolysis, the solvent is distilled off, getting selectarray polyvinyl alcohol in the form of a powder. An aqueous solution selectarray polyvinyl alcohols under certain conditions can also be sprayed using spray drying to obtain silence is containing a series of polyvinyl alcohol in the form of a powder. Obtaining powder selectarray polyvinyl alcohols described in the application DE-A 10232666. The most common drying methods are drying in the fluidized bed, drying in a thin layer, freeze drying and spray drying (spray drying).

Suitable for redispersing in water powder of the polymer (b) complex vinyl esters are those of carboxylic acids with 1 to 15 carbon atoms. To the preferred esters of this type include vinyl acetate, finalproject, vinylboronate, vinyl 2-ethylhexanoate, vanillaware, 1-methylphenylacetic, vinylbilt and vinyl esters α-branched monocarboxylic acids with 9 to 13 carbon atoms, for example the products VeoVa9®or VV10®(trade name for product of Shell company). Most preferred among them vinyl acetate.

It is suitable for use esters of methacrylic or acrylic acid include esters of these acids and unbranched or branched alcohols with 1-15 carbon atoms, such as methyl acrylate, methyl methacrylate, acrylate, methacrylate, propylacetate, propylbetaine, n-butyl acrylate, n-butylmethacrylate, 2-ethyl hexyl acrylate and norbornylene. Preferred among them are methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethyl hexyl acrylate.

As examples of olefins and dienes mononitate ethylene, propylene and 1,3-butadiene. It is suitable for use vinylaromatic compounds include styrene and vinyltoluene. From suitable for use vinylchloride can be called, among other things, vinyl chloride.

If necessary, you can also optionally copolymerizate auxiliary monomers in an amount of from 0.05 to 50 wt.%, preferably from 1 to 10 wt.%, in terms of the total weight of the basic polymer. Examples of auxiliary monomers are ethylene unsaturated mono - and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid, amides and NITRILES of ethylene unsaturated carboxylic acid, preferably acrylamide and Acrylonitrile, mono - and diesters of fumaric acid and maleic acid, such as their diethyl and diisopropyl esters, and also maleic acid anhydride, ethylene unsaturated sulfonic acids, respectively, and their salts, preferably vinylsulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid. As other examples are pre-stitched comonomers, such as ethylene polyunsaturated comonomers, such as divinerecipes, diallylmalonate, alismataceae or treelistener or secondary link comonomers, for example, acrylamidoglycolate acid (AGC), methyl is a new broadcast methylacrylamide acid (MAMAC), N-methylolacrylamide (N-MA), N-methylolmethacrylamide (N-MMA), N-metroselskabet, simple alkalemia esters, such as isobutoxide, or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolacrylamide. Suitable for use are also amoxilonline comonomers, such as glycidylmethacrylate and glycidylmethacrylate. As other examples may also be called creditentials comonomers, such as Acrylonitrile(alkoxy)- and methacryloxypropyl(alkoxy)silanes, vinyltriethoxysilane and fenilmetilketil, as alkoxygroup may be present, for example, remains ethers methoxy-, ethoxy and ethoxypropylamine. Mention should also monomers with hydroxy or CO groups, for example hydroxyalkyl esters of methacrylic and acrylic acids, such as hydroxyethyl-, hydroxypropyl - or hydroxyethylacrylate or-methacrylate, and also compounds such as diacetonitrile and acetylacetoneiminates or-methacrylate.

Examples suitable for use Homo - and copolymers are vinyl acetate, the homopolymers, copolymers of vinyl acetate with ethylene, copolymers of vinyl acetate with ethylene and one or more other complex vinyl esters, copolymers of vinyl acetate with ethylene and acrylic ester, copolymers of vinyl acetate is with ethylene and vinyl chloride, copolymers of styrene and acrylic ester, and copolymers of styrene with 1,3-butadiene.

Preferred are the acetate homopolymers, copolymers of vinyl acetate with 1 to 40 wt.% ethylene, copolymers of vinyl acetate with 1 to 40 wt.% ethylene and 1-50 wt.% one or more other comonomers from the group of vinyl esters with 1-12 carbon atoms in carbonisation residue, such as WikiProject, vanillaware, vinyl esters α-branched carboxylic acids with 9 to 13 carbon atoms, such as products VeoVa9®, VeoVa10®, VeoVa11®, copolymers of vinyl acetate with 1 to 40 wt.% ethylene and preferably 1-60 wt.% ester of acrylic acid with unbranched or branched alcohols with 1-15 carbon atoms, especially α-butyl acrylate or 2-ethylhexyl acrylate, and copolymers with 30-75 wt.% vinyl acetate, 1-30 wt.% vanillaware or vinyl ester α-branched carboxylic acids with 9-11 carbon atoms, and 1-30 wt.% ester of acrylic acid with unbranched or branched alcohols with 1-15 carbon atoms, especially n-butyl acrylate or 2-ethylhexyl acrylate, which additionally contain 1-40 wt.% ethylene, and copolymers of vinyl acetate with 1 to 40 wt.% ethylene and 1-60 wt.% vinyl chloride, with such polymers can additionally contain another, and the above-mentioned auxiliary monomers in the decree is the R quantities as indicated in wt.% values that define the content of each component in the composition of the corresponding copolymer, the amount in each case add up to 100 wt.%.

Preferable polymers of esters of (meth)acrylic acid, such as copolymers of n-butyl acrylate or 2-ethylhexyl acrylate or copolymers of methyl methacrylate and n-butyl acrylate and/or 2-ethylhexyl acrylate, copolymers of styrene and acrylic ester with one or more monomers selected from the group comprising methyl acrylate, acrylate, propylacetate, n-butyl acrylate, 2-ethyl hexyl acrylate, copolymers of vinyl acetate and of acrylic ester with one or more monomers selected from the group comprising methyl acrylate, acrylate, propylacetate, n-butyl acrylate, 2-ethyl hexyl acrylate and optionally ethylene, copolymers of styrene with 1,3-butadiene, with such polymers can additionally contain another, and the above-mentioned auxiliary monomers in the specified amounts, as indicated in wt.% values that define the content of each component in the composition of the corresponding copolymer, the amount in each case add up to 100 wt.%.

Monomers, respectively, the mass content of comonomers, choose with so that the glass transition temperature Twithas a rule, were in the range from -50 to +120°who, preferably from -30 to +95°C. the glass transition Temperature Twithpolymers can be defined in the usual way by the method of differential scanning calorimetry (DSC). Approximate values of glass transition temperature also can be pre-calculated using equation Fox (Fox). In accordance with the method of Fox (T.G. Fox, Bull. Am. Physics Soc. 1, 3, 1956, p.123) the glass transition temperature can be calculated by the following formula: 1/Twith=x1/Tc1+x2/Cu2+...+Xn/Tcnwhere Xndenotes the mass fraction (wt.%/100) of the monomer n, a Tcndenotes expressed in degrees Kelvin glass transition temperature of homopolymer monomer n. The values of glass transition temperature for homopolymers are listed in Polymer Handbook Handbook, 2nd ed., published by J.Wiley & Sons, New York, 1975.

Homo - and copolymers receive by well-known methods by polymerization in mass, polymerization in solution, the polymerization deposition polymer, suspension polymerization and emulsion polymerization. Preferred among these polymerization in solution, suspension polymerization and emulsion polymerization. The temperature of the polymerization generally ranges from 40 to 100°C, preferably from 60 to 90°C. When the copolymerization of gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride, the process can also carry out the od pressure, usually under pressure, comprising from 5 to 100 bar.

The initiate polymerization using commonly used for these purposes are soluble in water or soluble in the monomer initiators or combinations of redox initiators. Examples of water-soluble initiators are the sodium, potassium and ammonium salts peroxidizing acid, hydrogen peroxide, tert-beginprocset, peroxodisulfate potassium tert-butylperoxide, cumonherface, isopropylbenzaldehyde, azobisisobutyronitrile. Examples are soluble in the monomers, initiators are diacetylpyridine, dicyclohexylperoxydicarbonate, Dibenzoyl peroxide, tert-butylperoxybenzoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate. These initiators are usually used in amounts of from 0.01 to 10.0 wt.%, preferably from 0.1 to 0.5 wt.%, in each case, calculated on the total weight of the monomers.

As redox initiators used combinations of the above initiators in combination with reducing agents. Suitable for use with the reducing agents are the sulfites and bisulfite alkali metals and ammonium, for example sodium sulfite, the derivatives sulfoxylates acid, such as formaldehydeinduced zinc or alkali metals, such as hydrox methanesulfonate sodium, and ascorbic acid. The number used for these purposes, the reducing agent is usually from 0.01 to 10.0 wt.%, preferably from 0.1 to 0.5 wt.%, in each case, calculated on the total weight of the monomers.

When using the above as the preferred methods of suspension and emulsion polymerization is carried out in the presence of surface-active substances, such as protective colloids and/or emulsifiers. Suitable for these purposes, the protective colloids are, for example, partially saponified polyvinyl alcohols, polyvinylpyrrolidone, polyvinyl acetate, starches, cellulose and their carboxymethyl, methyl, hydroxyethylene and hydroxyproline derivatives. As usable emulsifiers can be termed as anionic and cationic, and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulphates with chain length from 8 to 18 carbon atoms, sulfates simple alilovic or alkylaryl esters containing from 8 to 18 carbon atoms in the hydrophobic residue and up to 60 ethylene or propyleneoxide units, alkyl - or alkylarylsulfonates with 8-18 carbon atoms, esters and palefire sulfonterol acids and monohydroxy alcohols or ALKYLPHENOLS, or nonionic surfactants, such as simple alkylpolyglycoside esters or simple alkylarylsulphonate esters, contain Asia to 60 ethylene-, accordingly, propylenoxide links.

The monomers can be pre-loaded into the reactor together, you can add together or you can download pre-defined portions, and the remainder be added after initiation of the polymerization. The addition can be performed separately (in space and time) or all added components or some of them to enter after pre-emulsification.

Upon completion of the polymerization of the residual monomers can be removed using known methods additional polymerization, for example, initiated by a redox catalyst for further polymerization. The remains volatile monomers can also be removed by distillation, preferably under reduced pressure and, if necessary, by passing through the system or on the system inert carrier gas, such as air, nitrogen or water vapor. The solids content in the resulting by such aqueous dispersions ranges from 30 to 75 wt.%, preferably from 50 to 60 wt.%.

To obtain holder in water polymer powders, aqueous dispersions, optionally after addition of protective colloids as contributing to the dispersion auxiliary agent, dried, for example, by drying in the fluidized bed, freeze-drying is whether spray drying. It is preferable to dry the dispersion by spray drying. Spray drying is carried out in the normal intended for these purposes installations for spraying dispersions can be used one-, two - or multi-component nozzles or rotary atomizers. The temperature output depending on the type of installation, the glass transition temperature of the resin and the desired degree of drying is usually chosen in the range from 45 to 120°C, preferably from 60 to 90°C.

When drying holder of polymer powders in water contributing to the dispersion auxiliary agent is usually used in an amount of from 3 to 30 wt.% in terms of the number of polymer components of variance. In other words, the total content of the protective colloid to the drying process should be at least 3 to 30 wt.%, preferably from 5 to 20 wt.%, in terms of the number of polymers.

Suitable for use as contributing to the dispersion auxiliary agent are partially saponified polyvinyl alcohols, polyvinylpyrrolidone, polysaccharides in water-soluble form such as starches (amylose and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethylene and hydroxyproline derivatives, proteins such as casein or Caseinate, soybean protein, gelatin, ligninsulfonate, sinteticheskimi, such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyfullerene demonomanie units, poly(meth)acrylamide, polyphenylsulfone acids and their water-soluble copolymers, melamineformaldehyde, naphthalenedisulfonate, copolymers of styrene, maleic acid and vinyl ether maleic acid. As contributing to the dispersion auxiliary agent, it is preferable to use only polyvinyl alcohols, which are both preferred protective colloids.

While the invention has been set and confirmed many times that when sprayed into the system it is advisable to add an antifoam in number, reaching 1.5 wt.% in terms of the amount of the basic polymer. To improve the stability during storage by increasing resistance to sticking, which refers primarily to the powders with a low glass transition temperature, to the resulting powders you can add the usual remedy against caking (anti-caking) in a 3-fold amount, preferably, however, up to 30 wt.%, in terms of the total weight of polymer components. As examples of such conventional anti-caking can be called calcium carbonate, respectively, magnesium, talc, gypsum, silicic acid, kaolin and silicates with largest the STU particles mainly from 10 nm to 10 μm.

The viscosity of the sprayed source material set by regulation of the content of solid substances so that its value was less than 500 MPa· (viscosity according to Brookfield at 20 revolutions and 23° (C), preferably less than 250 MPa·C. the solids Content in the sprayed dispersion is more than 15%, preferably more than 25%.

Powder coatings can be obtained by mixing the powder components a) and b). In one of the preferred embodiments of the invention to obtain a powder composition for coating an aqueous solution selectabase polyvinyl alcohol (a) and the aqueous polymer dispersion of the polymer (b), optionally after the addition of the protective colloid, the joint is subjected to drying, particularly preferably spray drying.

Components a) and b) are used in mass ratio (a constant value) from 99:1 to 1:99, preferably from 95:5 to 20:80, particularly preferably from 85:15 to 50:50, most preferably from 60:40 to 30:70.

Obtained according to the invention the products are used for coatings applied to the appropriate substrate (base) of paper or polymer films, materials-visual media designed for inkjet printing, such as paper and film. As substrates (basics), suitable for Nan is possible coatings, you can call the paper, the paper with the polymer coating on the basis of polyethylene, polypropylene, or polyethylene terephthalate (PET), as well as films of cellulose acetate, polyester film such as polyethylene terephthalate film, polyamide, polycarbonate, polyolefin, polyimide, polyvinyl acetate, polyester and polysulfonamide film.

During the formation of coatings on the substrate, in which the materials are used, intended for inkjet printing, coating compositions along with components a) and b) can also contain other binders and additives or these compounds can be used in combination with binders and additives in the formation of coatings on substrates, which serve as materials for inkjet printing.

As the most suitable for these purposes, additives and binders can be called cationic dispersing agents, such as polydiallyldimethyl-ammoniate, benzyldimethylammonium, dimethyldiallylammonium, copolymers with acrylamide, polymers modified with dimethylaminopyridine, polyoxyethylenesorbitan, dimethylaminoethylmethacrylate (DMAEM), polymers modified with chloride of methacryloxypropyltrimethoxysilane (MOUTH), cationic cellulose derivatives, cationic starch derivatives, cationic polyvinyl alcohols, polyeth linemen and its copolymers, compounds with trivalent ions of aluminum, boron and zinc chelate complex triethanolamine, titanium, copolymers of vinylpyrrolidone, polyamidoamine. Among binders include, for example, hydroxyethyl cellulose, starch, gelatin, casein, polyvinylpyrrolidone, dextran, dextrin, polyethylene glycol, agar, carrageenan, and xanthan gum.

It is suitable for application of plasticizers include, among others, ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin, simple onomatology ether of glycerol, monochlorohydrin glycerol, ethylene carbonate resulting, propylene carbonate, anhydride tetrachlorophthalic acid anhydride tetrabromophthalic acid, urea, phosphate, urea, triphenyl, glycerylmonostearate, propilenglikolmonostearata, tetramethylarsonium, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and sorbitol.

As pigments and fillers include, for example, silicic acid, calcium carbonate, clay, bentonite, aluminum oxide and titanium oxide.

As antispyware and auxiliary dispersant can be used, among other things, chloride of polydiallyldimethyl, benzyldimethylammonium, dimethyldiallylammonium, and equalization (the surface of) agents, podsvechivaya dyes, wetting, viscosity stabilizers, pH regulators, hardeners, the-absorbers, the oxidation inhibitors, optical brighteners and tabs dyes.

Recipe coating mass applied to paper and polymeric substrate, known to specialists in this field. To obtain the mass of the powder coating composition together or separate operations diluted with other components of the corresponding recipe in the required amount of water.

Examples

Paper coatings

Example 1

To obtain a product in this example used a joint spray drying a mixture of 70 wt.% (constant value) selectabase completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 6 MPa·and 30 wt.% (constant value) stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate with a particle size of 1 μm and a solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Example 2

In this example worked similarly to example 1, except that used selectarray polyvinyl alcohol whose viscosity is determined using a viscometer of Heppler in 4%aqueous solution, was 10 MPa·C.

Example 3

To obtain a product in this example used a mixture of the two taken in a mass ratio of 7:30 powders, one of which is selectarray completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 20 MPa·and the other redispersible polymer powder obtained from the stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate with a particle size of 1 μm and a solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Example 4

In this example worked similarly to example 1, except that before spray drying to the mixture was further added cationic dispersant. This cationic dispersant was mixed into the component a)+(b) mass ratio of between 5:45. The product is used in a coating weight of 45 mascectomy powder mixture with additional cationic dispersant and without it.

Comparative example 5

This example used a commercially available selectarray polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 25 MPa·C.

Comparative example 6

This example shows redispersible polymer powder obtained from the stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate, with a particle size of 1 μm, the content of solid substances is TBA 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Comparative example 7

To obtain a product used a mixture of water 11%by weight solution selectabase completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 20 MPa·and 45%stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate with a particle size of 1 μm and a viscosity according to Brookfield 500 MPa· (20 rpm).

The products presented in the examples and comparative examples were tested in the part below the coating weight of the paper:

precipitated silicic acid100 moschata
the mixture of example/EUR. example40 moschata
cationic dispersant5 moschata
the solids content in coating weight30%

As the base paper used the glued paper with a specific gravity of 80 g/m2when flow is applied to it coverage equal to 15 g/m2.

Test methods

The test for abrasion

The strip of coated paper with a width of 4.5 cm and a length of 19 cm was tested for abrasion in the corresponding device company Prufbau (system Dr. Turner) ispolzovaniya (weight 500 g) coated with a black paper for applications, reciprocating moving it across the strips 50 times. Retrieved on black paper the results were evaluated visually on a points system, where a score of 1 corresponds to 100%increase preservation of the black color, which means no signs of abrasion.

Whiteness

The degree of whiteness was determined by measuring the diffuse reflection filter (type R 457) and the results were evaluated visually on a points system, where a score of 1 corresponds to optimal index.

The test results (table 1).

Coverage analysisExample 1Example 2Example 3Example 4EUR. example 5EUR. example 6EUR. example 7
The test for abrasion111125*)
The degree of whiteness (R 457)5,15,25,15,15,612,3*)
*)Note: when using these solutions was not possible to obtain a coating composition with a solids content of 30 wt.%. Using a solution of modified polyvinyl is the first alcohol in a higher concentration of the storage stability was poor.

The coating of polymeric material

Example 8

To obtain a product in this example used a joint spray drying a mixture of 42 wt.% (constant value) selectabase completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 6 MPa·and 58 wt.% (constant value) stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate, with a particle size of 1 μm and a solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Example 9

In this worked example is similar to example 8, except that used selectarray polyvinyl alcohol whose viscosity is determined using a viscometer of Heppler in 4%aqueous solution, was 10 MPa·C.

Example 10

To obtain a product in this example used a mixture of the two taken in a weight ratio of 42:58 powders, one of which is selectarray completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 20 MPa·and the other redispersible polymer powder obtained from the stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate, with a particle size of 1 mm, the solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Example 11

In this worked example is similar to example 8, except that when spray-dried to the mixture was further added cationic dispersant. This cationic dispersant was mixed into the component a)+(b) mass ratio of between 8:85. The product is used in a coating weight of from 93 mascectomy powder mixture with additional cationic dispersant and without it.

Comparative example 12

This example used a commercially available selectarray polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 10 MPa·C.

Comparative example 13

This example shows redispersible polymer powder obtained from the stabilized polyvinyl alcohol functionalized dispersion of polyvinyl acetate, with a particle size of 1 μm and a solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

Comparative example 14

To obtain a product in this example used a mixture of water 11%by weight solution selectabase completely saponified polyvinyl alcohol with a viscosity determined using a viscometer of Heppler in 4%aqueous solution, 20 MPa·and 45%stable is th polyvinyl alcohol functionalized dispersion of polyvinyl acetate, particle size of 1 μm and a solids content of 45% and a viscosity according to Brookfield 500 MPa· (20 rpm).

The products presented in the examples and comparative examples were tested in the part below the coating weight of the paper:

precipitated silicic acid100 moschata
the mixture of example/EUR. example40 moschata
cationic dispersant5 moschata
the solids content in coating weight30%

The substrate (base) used is supplied by the promoter of adhesion of the PET film with a specific gravity of 90 g/m2when flow is applied to it coverage equal to 15 g/m2.

Test methods

The test for abrasion

A strip of film having a width of 4.5 cm and a length of 19 cm and coated were tested for abrasion in the corresponding device company Prufbau (system Dr. Turner) using a punch (weight 500 g) coated with a black paper for applications, reciprocating moving it across the strips 50 times. Retrieved on black paper the results were evaluated visually on a points system, where a score of 1 corresponds to 100%increase preservation of the black color, which means no PR the signs of abrasion.

Whiteness

The degree of whiteness was determined by measuring the diffuse reflection filter (type R 457) and the results were evaluated visually on a points system, where a score of 1 corresponds to optimal index.

The test results (table 2).

Coverage analysisExample 8Example 9Example 10Example 11EUR. example 12EUR. example 13EUR. example 14
The test for abrasion111135*)
The degree of whiteness (R 457)of 5.45,35,25,37,511,8*)
*)Note: when using these solutions was not possible to obtain a coating composition with a solids content of 30 wt.%. Using a solution of modified polyvinyl alcohol in a higher concentration of the storage stability was poor.

1. The application of the powder composition for coatings used as carriers of visual information materials what s inkjet, contains

a) one or more powder, selectarray polyvinyl alcohol-based fully or partially saponified copolymers of vinyl esters with a degree of hydrolysis of 75 to 100 mol.% and

b) one or more holder in water polymer powders based on homopolymers or copolymers of one or more monomers selected from the group comprising vinyl esters of unbranched and branched alkylcarboxylic acids with 1-15 carbon atoms, esters of methacrylic acid and esters of acrylic acid and alcohols with 1-15 carbon atoms, vinylaromatic compounds, olefins, diene and vinylchloride.

2. The use according to claim 1, characterized in that as component (a) use one or more powder selectarray polyvinyl alcohol-based fully or partially saponified copolymers of vinyl acetate.

3. The use according to claim 1, characterized in that selectabase polyvinyl alcohols obtained by copolymerization of one or more selectarray of comonomers in amounts of from 0.01 to 10 mol.%, selected from the group comprising ethylene unsaturated silicon compounds of General formula R1SiR20-2(OR3)1-3where R1denotes CH2=CR4-(CH)0-3or CH2=CR4CO2(CH2)1-3 , R2represents C1-C3alkyl residue, C1-C3CNS residue or a halogen, R3represents an unbranched or branched, optionally substituted alkyl residue with 1 to 12 carbon atoms or acyl residue with 2 to 12 carbon atoms, R3optionally can be interrupted by ether group, and R4represents N or CH3and including containing silane groups, (meth)acrylamide General formula CH2=CR5-CO-NR6-R7-SiR8m-(R9)3-mwhere m is 0-2, R5is either H or methyl group, R6represents H or alkyl group with 1-5 carbon atoms, R7represents alkylenes group with 1-5 carbon atoms or a bivalent organic group in which the carbon chain is interrupted by O - or N-atom, R8represents an alkyl group with 1-5 carbon atoms and R9is alkoxygroup from 1-40 carbon atoms, which may be substituted by other heterocycles.

4. The use according to claim 1, characterized in that as component (b) use one or more holder of polymer powders in water-based homopolymers or copolymers from the group comprising the acetate homopolymers, copolymers of vinyl is Zetta with ethylene, copolymers of vinyl acetate with ethylene and one or more other complex vinyl esters, copolymers of vinyl acetate with ethylene and acrylic ester, copolymers of vinyl acetate with ethylene and vinyl chloride, copolymers of styrene and acrylic ester, and copolymers of styrene with 1,3-butadiene, and the polymers can additionally contain auxiliary monomers.

5. The use according to claim 4, wherein the homopolymers or copolymers contain one or more auxiliary monomers of group (b)comprising ethylene unsaturated mono - and dicarboxylic acids, amides and NITRILES ethylene unsaturated carboxylic acids, mono - and diesters of fumaric acid and maleic acid, the anhydride of maleic acid, ethylene unsaturated sulfonic acids and their salts, ethylene polyunsaturated comonomers, acrylamidoglycolate acid (AGC), methyl ether methylacrylamide acid (MAMAC), N-methylolacrylamide (N-MA), N-methylolmethacrylamide (N-MMA), N-metroselskabet, simple alkalemia ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolacrylamide, glycidyl(meth)acrylate, (meth)Acrylonitrile(alkoxy)silanes, vinyltriethoxysilane and fenilmetilketil, as alkoxygroup may be the remains of ethers methods the sea, ethoxy and ethoxypropylamine, hydroxyalkyl esters of (meth)acrylic acid, diacetonitrile and acetylacetonates(meth)acrylate.

6. The use according to claim 1, characterized in that powder coatings are jointly drying aqueous solution selectabase polyvinyl alcohol (a) and an aqueous polymer dispersion b) if necessary, after adding a protective colloid.

7. The use according to claim 6, characterized in that the joint drying is conducted by a method of spray drying.

8. The use according to claim 1, characterized in that components a) and b) are used in a mass ratio (a constant value) from 95:5 to 20:80.

9. The use according to claim 1 in the compositions of the coatings on the basis of paper, paper coated with a polymer coating, polymer films and materials for inkjet printing.

10. The use according to claim 9, wherein the powder composition for coatings together or separate operations diluted with other components of the corresponding recipe in the required amount of water.



 

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FIELD: printing materials.

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FIELD: image generation.

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FIELD: method and device for colored flexography.

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7 cl, 5 dwg

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