Using whitening pigments in compositions for coating paper cover

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

 

The present invention relates to the use of bleaching of pigments for coating compositions, coated paper.

Aqueous coating compounds are widely used in the production of papers and boards with a coating. Compositions for coatings used for the purpose of bleaching, usually contain anionic fluorescent whitening agents, which strongly depends on the number and nature of the used binders. The use of cationic formulations for coatings, for example, in the case of paper for inkjet printers, leads to loss of effect, for example, to poor svetostoyjkostj, to spread under the action of the foodstuffs or a deterioration in the print quality. Similar problems can also occur in the case of cellulose or use in the molding.

Currently, it has been unexpectedly discovered that some whitening pigments containing melamine-formaldehyde resin and a water-soluble fluorescent whitening agent, significantly improves the properties of the compositions for coatings.

The present invention relates also to the use of bleaching of pigments, including:

(a) a condensation product of melamine and formaldehyde or phenol and formaldehyde and

b) a water-soluble fluorescent whitening agent for coating compositions, coated paper.

Products con is Ansatie melamine and formaldehyde, also referred to as melamine-formaldehyde (MF) resins, are aminoplastic resins.

Mentioned condensation products are formed during the acid catalyzed or base interaction of melamine with aqueous solutions of formaldehyde in the reaction of oxymetholone, with the formation of N-oxymethylene compounds. With increasing reaction time or temperature increases, oxymethylene groups react with additional melamine, forming methylene bridges or, if oxymethylene groups react with each other, essential oxymethylene bridges.

The reaction usually stops at the stage when the initial condensation products, which can dissolve or melt, which, if desired, can be mixed with fillers. To increase the solubility of these preliminary condensation products, some oxymethylene groups can be etherification.

Substance initial stages of the reaction can be called an aqueous solution, which can be entered fluorescent whitening agent. Etherification of the N-oxymethylene compounds may also be conducted, after azeotropic distillation of water with alcohols or after spray drying, by tarifitsirovana practically anhydrous oxymethylene lower alcohols, with the addition of acidic or alkaline cat is of catalysts, natalizumab after the esterification, and, if appropriate, by distillation of the excess alcohol.

In a further embodiment, the polycondensation of formaldehyde with forming the aminoplast melamine or phenol is carried out in the presence of a fluorescent whitening agent.

Fluorescent whitening agents corresponding to component (b) and is applicable for use in this invention correspond to the formula

where

R1and R2, independently of one another, are-OH, -Cl, -NH2, -O-C1-C4alkyl, -O-aryl, -NH-C1-C4alkyl, -N(C1-C4alkyl)2, -N(C1-C4alkyl)(C1-C4hydroxyalkyl), -N(C1-C4hydroxyalkyl); or-NH-aryl, for example, aniline-, aniline-mono - or di-sulfonic acid or uninsulated, morpholino-, -S-C1-C4alkyl(aryl) or a radical of amino acids, for example, aspartic acid or iminoxyl acid, which is substituted by a radical in the amino group, and M is hydrogen; sodium; potassium; calcium; magnesium; ammonium; mono-, di-, tri - or Tetra-C1-C4alkylamino; mono-, di - or tri-C1-C4hydroxyethylamine; or ammonium di - or tizamidine a mixture of C1-C4alkyl and C1-C4hydroxyalkyl groups.

Particularly suitable fluorescent bleach is who are the agents of the formula (1) are such where the group R1- aniline radical, especially those where R2- NH-C1-C4alkyl, -N(C1-C4alkyl)2, -N(C1-C4alkyl)(C1-C4hydroxyalkyl), -N(C1-C4hydroxyalkyl)2morpholino or amino acid radical, for example, aspartic acid or iminoxyl acid, which is substituted by a radical in the amino group, and M is hydrogen, sodium or potassium.

C1-C4the alkyl radicals can be branched or unbranched, for example, methyl, ethyl, propyl, isopropyl or n-butyl; they can be or not be, substituted with halogen, for example fluorine, chlorine or bromine, C1-C4alkoxy radicals, for example methoxy - or ethoxy-, phenyl or carboxyla, C1-C4alkoxycarbonyl, for example, acetyl, mono - or di-(C1-C4alkyl) amino or a group-SO3M.

The compounds of formula (1) are used, preferably in a neutral way, that is, M is preferably a cation of an alkali metal, mainly sodium.

Fluorescent whitening agents corresponding to component (b)are present in otbelivayushe the pigment for use in this invention in amounts of from 0.05 to 10 weight %, preferably from 0.1 to 5 weight %.

Whitening pigments used in accordance with this invention, t is the train to contain, in addition to the melamine-formaldehyde or phenol-formaldehyde resin, additional copolymers (component (C)), for example, aromatic sulfonamides, cyanurate acids, urea, cyclic ureas, for example, edilmesini, or glyoxalase acid.

Preferably, the bleaching of the pigments used in this invention also include copolymers with aromatic sulfonamide.

Preferably, the product is a melamine-formaldehyde polycondensation is used as component (a).

Whitening pigments for use in this invention are prepared in different ways. One way they can be prepared in the melting process, the procedure is the following:

The aromatic sulfonamide is melted in a suitable reaction vessel. Then molten sulfonamide slowly added formaldehyde. Forms a low-melting resin. Then, when the reaction is finished, the resin embarks on further interaction with melamine. Happens deposition, and forms a resin having a relatively high melting point between 115°C to 135°C. At the end of the interaction is added to the reaction mixture of fluorescent whitening agent. A resinous reaction mixture is served in droplet form at a temperature of from 150 to 175° With in a suitable container, where it remains cool.

Then, glassy resin is ground, using appropriate equipment, to a particle size of about 3 mm, the Resulting material then is introduced into a suitable apparatus for grinding, for example in ball, vibration or hammer mill, where the particle size of the resin is brought to 5-6 μm.

In an additional embodiment, bleaching pigments can be prepared in water during the process, the procedure of which is presented below:

Whitening pigment used in accordance with the present invention, is prepared by mixing components (a) and (b), preferably in the presence of a solvent, mainly water. Component (a) is used preferably in the form of a preliminary product of condensation or N-oxymethylene derived low molecular weight. If desired, after mixing, the solvent can be removed.

Then the pigments are dried, crushed and, optionally, re-dispersed in water for further use.

Whitening pigments used in accordance with the present invention preferably contain:

(a) from 75 to 99 wt.%, preferably from 85 to 95 wt.%, product melamine-formaldehyde or phenol-formaldehyde polycondensation,

(b) from 0.05 to 5 wt.%, preferably from 0,to 5 wt.%, water-soluble fluorescent whitening agent and

(c) from 0 to 20 wt.%, preferably from 5 to 10 wt.%, aromatic sulfonamida.

Finally shredded whitening pigments in powder form may, after dry grinding, to be included in the composition for coating paper, the particle size is from 0.05 to 40μm, preferably from 0.3 to 10 μm, more preferably from 0.5 to 5 μm.

First and foremost, however, it would be more convenient dispersing finely divided whitening pigments in an aqueous medium and to enable the final aqueous dispersion in the coating composition for paper.

The amount of bleaching of the pigments for use in accordance with the present invention, applicable in the composition for coating paper, depends on the desired bleaching effect; usually, this amount is from 0.01 to 5% by weight from the pure active substance, based on the use of melamine-formaldehyde or phenol-formaldehyde polycondensation product.

Compositions for coating paper typically have a solids content of 35 to 80 wt.%, preferably from 40 to 70 wt.%. In addition to bleaching pigment according to this invention, they typically contain (all quantities relative to the pigment):

(i) 100 parts by weight of inorganic pigment,

(ii) from 3 to 25 parts by weight of filler, of which not battelino, half can be natural (i.e. non-synthetic) with fillers, such as casein, starch,

(iii) up to 1 weight parts of a thickener,

(iv) to 2 parts by weight of a moisture resistant agent.

Bleaching of the pigments according to this invention, particularly suitable for bleaching, optional, pigmented formulations for coatings, commonly used in the textile, pulp and paper, dyeing industry, adhesives and plastics. As fillers (fillers) such compositions for coatings contain dispersions of plastics on the basis of copolymers of butadiene and styrene, Acrylonitrile, butadiene and styrene, esters of acrylic acid, ethylene - vinyl chloride and ethylene - vinyl acetate, or homopolymers, such as polyvinyl chloride, grades, polyethylene, polyvinyl acetate or polyurethane.

For the purposes of pigmentation in compositions for coatings typically used aluminum silicates, such as China clay or kaolin and barium sulfate, white satin, titanium dioxide or calcium for the paper. As examples of these are described in the work J.P.Casey "Pulp and Paper; Chemistry and Chemical Technology, 2ndEd. Vol.III, p.1648-1649 and in Mc Graw-Hill "Pulp and Paper Manufacture" 2ndEd. Vol.II, p.497 (Jai, "Pulp and paper, Chemistry and hightechnology" 2nd edition, volume III, str-1649 and MC grow-hill, "Pulp and paper manufacture" 2 and the creation, volume II, str) and in the patent EP-A-0003568.

Bleaching of the pigments according to this invention can be used for coating paper, especially for inkjet paper and photo paper, wood, textiles and nonwovens, films and suitable building materials, foil. Particular preference is given to using paper and cardboard, and paper.

Covering or coating, thus obtained, have, in addition to high svetostoyjkostj, excellent degree of whiteness. Uniformity, smoothness, volume and suitability for printing is also improved, because bleaching pigments used in accordance with this invention, remain in the matrix as additional fillers and have a favorable effect on the suitability of the paper for printing.

The invention is illustrated in the following examples.

Example 1: Preparation of a whitening pigment

1.5 g of the active substance, the fluorescent whitening agents of the formula

mix in a glass container with 15 g of 60% aqueous solution of intoximeter-melamine 21/2methyl ether (=LYOFIX CHN), then diluted with 120 g of deionized water and heated to 50°With water bath under stirring.

The deposition is conducted at a pH from 5 to 4.0 using 2N sulfuric acid. Heating continued until 85-90°and then the temperature is maintained for 10 minutes. Within 15 minutes the pH is brought to 10,0-11,0 using 30% aqueous sodium hydroxide solution. The mixture is then cooled, filtered on a Buechner funnel with a glass filter and dried for 2 hours at 60°C. Gravimetrically particular output is approximately 70% (±1,5).

Example 2: Preparation of composition

Whitening pigment prepared in Example 1, homogenized and korrektiruete by the method of wet grinding in a mill with glass balls for 2 hours. The composition includes the following pieces:

ProductThe amount in gramsNumber percentage
Whitening pigment4,515
Polyviol V03/+40(PVA)25,5 (5%solution)4,25
Deinotheriinae water(from solution Poliviou)80,75
Only30,0100,0
Glass balls50,0
Just grinding media80,0

Examples of the application

3 parts of the composition prepared in Example 2, in terms of dry substance, to aplauda to the composition for coating, consisting of 60 parts of caso3and 40 parts of kaolin, playing the role of pigment coating, and 1 part of polyvinyl alcohol in the role of additives to the binder and 5 parts of a styrene-butadiene binder.

Devoid of wood paper covered with a composition for coating in the amount of 12 grams per square meter. Fluorescence (ISO) and whiteness (CIE), measured after drying, amount to 6.9 and 92, respectively, when using the whitening agent of the formula (2), and 9.0 and 100, respectively, when using the whitening agent of the formula (3). Coating without the addition of pigment shows fluorescence 0 and whiteness of 70.

A. Obtaining bleaching of pigments

Whitening pigment according to the invention (I) was obtained as described in Example 1 of the present invention, and using a fluorescent whitening agent of the formula

Comparative pigment (I*) no GB 2284889 was obtained by the reaction of a suspension of 10.0 g of the product of the condensation of urea/formaldehyde (Pergopack(M2) is 60.0 g of water with 0.187 g of the fluorescent whitening agent of formula (4)

essentially, as described on page 12, Examples 1-8 (GB 2284829).

C. preparation and use of compositions for coating

To coloring the coating containing 60 weight. parts of calcium carbonate, 40 weight. parts of kaolin, 9 weight. parts styrene/butadiene latex dispersion is AI (calculated on the dry matter), 0,25 weight. parts of the rheological modifier (polyacrylic acid copolymer, polyacrylamide) and 0.2 weight. part of polyvinyl alcohol was added various amount of bleaching of the pigments (I) and (I*), respectively. Then the mixture was stirred for 15 minutes to ensure homogeneity.

Coloring coating is then applied to paper with bestevenner base containing no fluorescent whitening agent and which has a weight of 90 g/m2using laboratory manual installation for coating so that after drying, the coating weight in the result was approximately 12.5 g/m2.

C. Results

Fluorescence and white (with and without UV light) of the resulting securities were measured by Spectroflash 30GO spectrophotometer and calculated the corresponding values of white. These results are summarized in the following Table 1.

Table 1
PigmentFluorescence ISOWhite without UVWhite with UVWhite CIE
4 part (I)12,888,0100,8113,1
3 part (I)11,8of 87.899,6109,9
1.5 parts (I)8,9 87,696,5102,1
3 part (I*)4,6to 85.290,088,0

The results presented in Table 1, clearly demonstrate the superiority of the whitening effect of the pigment (I) according to the invention compared with the same pigment (I*no GB 2264829 A.

1. Composition for coating a coated paper, comprising the whitening pigment containing

(a) the product melamineformaldehyde or phenol-formaldehyde polycondensation, and

(b) a water-soluble fluorescent whitening agent of the formula

where R1and R2, independently of one another, are-OH, -Cl, -NH2, -O-C1-C4alkyl, -O-aryl, -NH-C1-C4alkyl, -N(C1-C4alkyl)2, -N(C1-C4alkyl)(C1-C4hydroxyalkyl), -N(C1-C4hydroxyalkyl)2or-NH-aryl, for example, aniline, Unionman or desulfonema acid or uninsulated, morpholino-, -S-C1-C4alkyl(aryl) or a radical of amino acids, for example, asparginase acid or iminoxyl acid, which is substituted by a radical in the amino group, and

M is hydrogen; sodium; potassium; calcium; magnesium; ammonium; mono-, di-, tri - or Tetra-C1-C4alkylamino; mono-, di -, or three-From -C4hydroxyethylamine; or ammonium di - or tizamidine a mixture of C1-C4alkyl and C1-C4hydroxyalkyl.

2. The composition according to claim 1, where the fluorescent whitening agent corresponds to the formula (1)in which R1- aniline radical and R2and M have the meanings indicated in claim 1.

3. The composition according to claim 2, where the fluorescent whitening agent corresponds to the formula (1)in which R2- NH-C1-C4alkyl, -N(C1-C4alkyl)2, -N(C1-C4alkyl)(C1-C4hydroxyalkyl), -N(C1-C4hydroxyalkyl)2morpholino - or a radical of amino acids, for example, asparginase or iminoxyl acid, which is substituted by a radical in the amino group, and M is hydrogen, sodium or potassium.

4. The composition according to any one of claims 1 to 3, where component (a) is a product melamineformaldehyde polycondensation.

5. The composition according to any one of claims 1 to 4, wherein the fluorescent whitening agent (b) is present in otbelivayushe the pigment in an amount from 0.05 to 10 weight. %.

Casta according to any one of claims 1 to 5, where the whitening pigment contains as an additional component (C) up to 20% of a copolymer of an aromatic sulfonamide.

7. The composition according to any one of claims 1 to 6, where dry whitening pigment has a particle size of from 0.05 to 40 μm.



 

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34 cl, 9 tbl, 2 ex

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FIELD: organic chemistry, paper industry.

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7 cl, 1 tbl, 3 ex

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2 cl, 4 ex

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