DE2242597A1 - Optical bleaches dissolved in org liquids - esp softeners for textiles and paper-coating compsns - Google Patents

Abstract

A prepn. for whitening fibrous materials and coating compsns. for paper is a soln. of (a) an optical dispersion bleaching agent in (b) a colourless, water-immiscible org. liquid with b.pt. >150 degrees C and in which the whitening agent has solubility is not 0.3 g/litre at room temp. Treatment is under mild conditions. The whitening effect is fast to washing. Wool can be given a durable bleach.

Description

Whitening Preparations The invention relates to preparations for tinting white of coating weights for papers, which are characterized by the fact that they are the solution a dispersion brightener (a) contained in such an organic liquid (b), which is immiscible with water, the boiling point of which is above 150 ° C and in which the whiteners have a minimum solubility of 0.3 g per liter at room temperature have, wherein the solution can optionally also contain an emulsifier.

The invention also relates to a method for whitening coating slips for papers, which is characterized in that the coating slips solutions of dispersion brighteners (a) in colorless, organic liquids (b) added, which are immiscible with water, the boiling point of which is above 1500C and in which the whiteners have a minimum solubility of 0.3 g per liter at room temperature have, wherein the solutions can optionally also contain an emulsifier.

As a representative of the solvents used in the preparations according to the invention organic liquids to be used for the whiteners are, for example called: high-boiling ethers, such as dibenzyl ether, diphenyl ether and 1-methoxymethyl-napthalene; However, liquid plasticizers that are colorless, are odorless, water-resistant, lightfast and not very volatile and are neutral in water react.

The plasticizers characterized by these properties can belong to the most diverse types of plasticizers; z.

Phosphoric acid esters, such as diphenyloctyl phosphate, trichloroethyl phosphate or trioctyl phosphate; Monocarboxylic acid esters such as oleic acid methyl ester; Oxycarboxylic acid esters, such as acetyl (2-ethylhexyl) citrate, acetyl tri-n-butyl citrate or castor oil; Aryl alkanesulfonates, such as phenyl dodecanesulfonate or cresyl tetradecanesulfonate; Acetals, such as diphenoxyethyl formal; chlorinated hydrocarbons, such as chlorinated paraffins with a chlorine content of 40 - 50%; epoxidized fatty acids such as epoxidized soybean oil or epoxidized flaxseed oil; polymeric esters such as polyglycolic adipate or phthalic acid polyethylene glycol ester; Alkylbenzenes such as dodecylbenzene.

Dicarboxylic acid ester plasticizers, such as adipic acid dinonyl ester, have proven particularly useful. Adipic acid dioctyl ester, sebacic acid dibutyl ester, sebacic acid dioctyl ester and especially phthalic acid esters, such as phthalic acid dibutyl ester, phthalic acid dinonyl ester and benzyl butyl phthalate.

In the context of the invention, dispersion brighteners are water-insoluble or optical brighteners that are sparingly soluble in water are understood. These can be of the most varied Belong to compound classes, the only requirement is that they do not have any water-solubilizing agents Groups included. As representatives of the preparations and methods according to the invention Dispersion brighteners to be used are, for example: naphthalic acid imide derivatives, such as 4-methoxy-N-methylnaphthalimide or 4- [3'-methylpyrazolyl- (1 ')] -N-ethylnephthalimide; Styryl-triazole derivatives such as 2-styryl-naphthotriazole, 2-styryl-5- [5'-methyl-6'N-butoxy-benzotriazolyl- (1 ')] -benztriazole or 2- [4'-phenylatyryl] -5-methoxybenzotriazole; Distyryl derivatives such as 1,4-bis (2-cyanstyryl) benzene; Syrazoloquinoline derivatives such as 15-dimethyl-4-chloropyrazolo- (3, 4-b) -quinoline; Pyrene derivatives, such as 2,4-dimethoxytriazinyl- (6) -pyrene; Benzoxazole derivatives, such as 1,2-ethylene-bis-5,5'-methyl-benzoxazole, 5-tert-butyl-2- (diphenylstyryl) -phenyl-benzoxazole, 4,4'-bis- [5-phenyloxazolyl- (1)] -diphenyl or 2,5-bis- [benzoxazolyl- (2)] thiophene; tyrazoline derivatives, such as 1- (4'-aminosulfonylphenyl) -3- (4'-chlorophenyl) pyrazoline, 1- (4'-methylsulfonphenyl) -3- (4'-chlorophenyl) pyrazoline or 1- {2 '- [3rt-dimethylaminopropyl- (2 oxy] sulfonyl} -3- (4'-chlorophenyl) pyrazoline; Carboetyril derivatives, such as 3-phenyl-7-dimethylamino-N-ethylcarboetyril.

Have proven particularly effective in the preparations according to the invention and Process Coumarin-type dispersion brighteners such as: 3-phenyl-7-6-cSor-4-diethyleminotriazingl- (2) J -aminocoumarin, 3-phenyl-7-ethylcarbamoylcoumarin, 3- [pyrazolyl- (1 ')] - 7- [4'-methyl-5'-phenyltriazolyl- (2')] coumarin, 3- [4'-chloropyrazolyl- (1 ')] - 7- [3'-methylpyrazolyl- (1')] -coumarin, 3- [4'-chloropyrazolyl- (1 ')] - 7- [4'- methyl-5'-phenyl-triazolyl- (2 ')] - coumarin, 3- [pyrazolyl- (1)] - 7-naphtho- [1 ', 2'; 4,5] -triazolyl- (2) -coumarin and in particular 3-phenyl-7- [4'-methyl-5'-phenyl-triazolyl- (2 ')] -coumarin.

The preparations according to the invention or the method according to the invention are suitable for the optical brightening of those commonly used in the paper industry Coated corns, specifically for lightening unplagmented, but in particular pigmented litter. These known coating slips contain binders Plastic dispersions based on copolymers of butadiene-styrene, acrylonitrile-butadiene-styrene, Acrylic acid esters, ethylene vinyl chloride and ethylene vinyl acetate; Homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene and polyvinyl acetate; or Polyurethanes.

Aluminum silicates are usually used to pigment the coating slips like china clay and kaolin, also barium sulfate, Satin white, titanium dioxide and calcium carbonate (chalk). Formulations of such known coating slips for paper are for example in J. P. Casey "Pulp and Paper; Chemistry and Chemical Technology", 2nd Edition, Vol. III, pages 1648 to 1649 and in McGraw-Hill "Pulp and Paper Manufacture", 2nd Edition, Vol. II, page 497.

The preparation of the preparations according to the invention is advantageously so made that the dispersion brighteners, optionally with heating 40 to 100 ° C, dissolves in the organic liquids and then the solution optionally mixed with an emulsifier. The use of emulsifiers is recommended when the brightener solutions are to be used in aqueous systems The solutions obtained in this way, or when used, are used to lighten the coating slips the mixtures obtained from emulsifiers, directly from the aqueous coating slips added. The amount of whitener preparation used for lightening may vary depending on the the desired lightening effect vary within wide limits; in general one will the preparations in an amount of 20 to 200 g, preferably 40 to 100 g per kg of coating mass insert.

To dissolve the brightener, usually for one part by weight Brighteners 10 to 1,000, preferably 20 to 250, parts by weight of organic liquid needed.

Anionactive, non-ionic or ampholytic emulsifiers can be used Emulsifiers are used.

Examples of anionic emulsifiers are: a) Carboxylic acids and their salts, such as the sodium, potassium or ammonium salts of the Laürin-, Stearin- or oleic acid, acylation products of aminocarboxylic acids and their Salts, e.g. B. the sodium salt of oleoyl sarcoside.

b) sulfates such as fatty alcohol sulfates, e.g. B. Lauryl sulfate and Lorol sulfate, Sulfates of hydrofatty acid esters, e.g. B.

sulfated castor oil, fatty acid hydroxyalkylamides, e.g. B. sulfated tokosfettsäureäthanolamid as well as sulfates of partially esterified or etherified Polyhyroxy compounds, such as sulfated oleic acid monoglyceride or olcerol ether sulfate, also sulfates substituted polyglycol ethers, z. B. Nonylphenol polyglycol ether sulfate.

c) sulfonates such as primary and secondary alkyl sulfonates, e.g. B.

C12-C16 paraffin sulfonic acids or their sodium salts, alkyl sulfonates with amide or ether-like bonded acyl radicals such as oleyl methyl tauride and Sulfonates of polycarboxylic acid esters such as di-iso-octyl sulfate succinic acid ester; further soiche with aromatic groups such as alkylbenzene, z. B. dodecylbenzene, alkylnaphthalene, such as dibutylnaphthalene and alkylbenzimidazole sulfonates, such as tetradecylbenzimidazole sulfonates.

Examples of non-ionic emulsifiers that may be mentioned are: First and ethers of polyalcohols such as alkyl polyglycol ethers, e.g. B. lauryl alcohol or Oleyl alcohol, polyethylene glycol ethers, acyl polyglycol ethers such as oleic acid polyglyco ethers, Alkylaryl polyglycol ethers such as the ethoxylation products of nonyl and dodecyl phenol, acylated amino-alkanol polyglycol ethers, also the known non-ionic teneids, which differ from fatty amines such as stearylamine, fatty acid amides or from sugars and their Derive derivatives.

Examples of ampholytic emulsifiers that may be mentioned are: alkylbetaines such as dodecyl-dimethyl-aminossetic acid, sulfobetaine, such as stearyl-dimethyl-ß-aminopropane-sulfonic acid, Aminocarboxylic acids or ampholytes obtained from cation-active compounds by introduction from acid residues, such as oleylamino-ethyl-dimethyl-aminosetic acid.

The amounts of emulsifiers can vary within wide limits; in general has it proven useful, 0.5 to 200, preferably 1 to 70 percent by weight of emulsifier, based on the weight of the plasticizer.

With the help of the whitener preparations according to the invention it is possible to achieve the Significantly increase the whiteness of coating slips for paper and cardboard. With the water-soluble optical brighteners previously used in the paper industry effective optical brightening of the coating slips was only possible if if these contain an addition of natural binders such as starch, casein or carbomethyl cellulose, or water-soluble compounds such as polyvinyl alcohol. Polyvinylpyrrolidone or Contained higher molecular weight polyethylene glycols.

In the coating slips for paper, however, are increasingly synthetic binders, d. h, plastic dispersions, used as a sole binder and there was therefore the technical task of finding brightening agents for these. With With the help of the Weisstäner preparations according to the invention, it is now possible, even in spreads, the only synthetic binders and no natural binders or water-soluble Compounds contain more to achieve excellent whitening effects, while also With high additions of whitener, no graining due to oversaturation of the material with brightener In the examples below The parts specified are parts by weight, unless otherwise specified.

Bei8Plel 1 40 parts of the whitener preparation described below 10000 parts of a coating slip of the following composition are used: 300 parts of aluminum silicate (China clay) 1 part of sodium polyphosphate 120 parts of a paper coating slip Usual 50% aqueous plastic dispersion based on a butadiene-styrene copolymer 420 parts of water were added. This coating mass, the pH of which is around 8.5, is applied to sized paper, unsized paper and cardboard by means of a usual Applicator applied, a line is applied to all three types of paper treated obtained, which is characterized by an excellent degree of whiteness.

The whitening preparation used was made as follows: 5 parts 3-Phenyl-7- [4'-methyl-5'-phenyl-triazolyl- (2 ')] -coumarin were stirred and dissolved in 925 parts of benzyl butyl phthalate while heating to about 80 ° C. In these 70 parts of C12-C16 paraffin sulfonate were then stirred into the solution.

Example 2 80 parts of the whitener preparation described below are looo parts of a coating mass of the following composition: 400 Parts china clay 50 parts barium sulfate 250 parts calcium sulfoaluminate (satin white) (20% strength aqueous suspension) 200 parts of a 50% strength customary for paper coating slips aqueous plastic dispersion based on an acrylic acid ester copolymer 430 Parts, water added. The coating mass, the pH of which is around 9.5, is on sized paper, unsized paper and cardboard using a conventional applicator upset.

An excellently lightened line is seen on all three types of paper obtain.

The whitening preparation used was made as follows: 5 parts 3-Phenyl-7- [4'-methyl-5'-phenyl-triazolyl- (2 ')] -coumarin were stirred and dissolved in 745 parts of diphenyloctyl phosphate with heating to about 80 ° C. In these 20 parts of dodecylbenzenesulfonate were then stirred into the solution.

An equally lightened line is obtained if instead of the whitener preparation used, the same amount of one of those described below Whitener preparations a), b) or c) are used: Preparation a): 7 parts of 2,5-bis- [benzoxazolyl- (2)] thiophene were stirred and heated to 70 to 8000 in 800 parts of sebacic acid dibutyl ester solved. In the solution were then 15 parts of C12-C15 paraffin sulfonate and lo parts of lauryl alcohol sulfonate are stirred in. An equivalent preparation was obtained when, instead of the dibutyl sebacate, the same amount of dioctyl sebacate was used.

Preparation b): 5 parts of 3- [4'-chloropyrazolyl- (1 ')] - [4'-methyl-5'-phenyltriazolyl- (2') 7-coumarin were added to 700 parts of dinonyl adipate with stirring and heating to 7 ° to 80 ° C solved.

20 parts of lauryl alcohol sulfate were then stirred into the solution. An equivalent preparation was obtained if instead of the adipic acid dinonyl ester the same amount of dioctyl adipate was used.

Preparation c): 5 parts of 3-phenyl-7- [4'-methyl-5'-phenyl-triazolyl- (2 ')] -coumarin were dissolved in 600 parts of chlorinated paraffin (Cl content: 40%). In the solution were Then stir in 15 parts of nonylphenol decapolyethylene glycol ether.

Example 3 80 parts of the whitener preparation described in Example 1 are 1000 parts of an approximately 50% aqueous solution customary for paper coating slips Polyurethane dispersion added. The coating slip obtained in this way is glued onto Paper, unsized it is applied to paper and cardboard by means of a conventional application device. Well-brightened lines are obtained.

Claims (9)

Patent claims 1.) Preparations for whitening coating slips for paper, thereby characterized in that it contains the solution of a dispersion brightener (a) in such contain colorless organic liquid (b) which is immiscible with water, whose boiling point is above 150 ° C and where the whiteners are at room temperature have a minimum solubility of 0.3 g per liter. 2.) Preparations according to claim 1, characterized in that the solutions also contain an emulsifier (c). 3.) Preparations according to claim 1 and 2, characterized in that the solutions contain Eomponenten (a) and (b) in a weight ratio of 1: lo to looo. 4.) Preparations according to claim 1 to 3, characterized in that the solutions contain the 'components (a) and (b) in a weight ratio of 1:20 to 25o. 5.) Preparations according to claim 2 to 4, characterized in that the solutions o, 5 to 200 percent by weight of emulsifiers, based on the weight of the Component (b) included. 6.) Preparations according to claim 2 to 5, characterized in that the solutions 1 to 70 percent by weight of emulsifiers, based on the weight of the component (b) included. 7.) Process for whitening coating slips for papers, thereby characterized in that the coating slips solutions of dispersion brighteners (a) in such colorless organic liquids (b) clogged, which with water does not miscible are whose boiling point is above 150C and in which the whiteners are at room temperature have a minimum solubility of 0.3 g per liter. 8.) Process according to claim 9, characterized in that one solutions used, which in addition to components (a) and (b) also contain an emulsifier (c). 9.) Papieratreichmassen lightened by the method according to claim 7 and 8.