DE1902459A1 - Optically brightened fibre fleeces - Google Patents

Abstract

Fleeces based on natural and/or synthetic fibres contain a binder-mixed polymerisate of a minor amount of 1, 3-diphenyl - DELTA2-pyrazine monomer in which the phenyl groups are optionally substituted and the pyrazolinenucleus is substituted with a group R wherein R is H or lower alkyl and with a group -(Y)m-A-(CH2)n-Eo-(Y)p-c (CH2)gH =CH2 wherein Y is - CO- or -CH2-, A is -O- or -NH-, E is -O-, -NH-or -NR1- in which R1 is alkyl, n is 2-6, m,n,o,p and q are O and/or l and a major amount of a further olefinic unsaturated monomer.

Description

Process for the production of optically brightened nonwovens The The invention relates to a method for producing optically brightened fleece substances using at least one crosslinkable copolymer as a binder, which contains an optical brightener in polymerized form.

It is known that nonwovens are made using natural rubber latices or to prepare aqueous dispersions of synthetic copolymers. Such synthetic copolymers are e.g. in DAS 1 134 353, 1135 412, 1986 208, 1,219,227 and 1,159,384, U.S. Patents 3,110,292, 2,931,749 and 2,982,682, the English patents 914 714 and 867 545 or the Belgian patent specification 654 817. They are made from acrylic and methacrylic acid esters, as well as butadiene, Styrene, polyvinyl acetate and the like built up. The copolymers can contain functional groups that act upon pH change or at elevated temperature Entering condensation reactions, whereby crosslinked and thus against organic solvents more stable copolymers are obtained.

The optical brightening of nonwovens can be achieved by adding a water-soluble optical brightener for the impregnation liquor in the manufacture of the nonwoven fabric or according to the method of patent application P 17 69 742.6 (O.Z. 25 664) by using of binders which contain an optical brightener in polymerized form. The disadvantage of using water-soluble brighteners is that they are used in laundry and can be washed out of the nonwoven fabric after chemical cleaning. With the copolymerized optical brighteners of patent application P 17 69 742.6 (O.Z. 25 664) is used in acrylonitrile or methacrylonitrile-containing copolymers as binders, at most one insufficient Brightening achieved.

It has now been found that optically brightened fiber nonwovens based on natural and / or synthetic fibers and binder copolymers which carry optically brightening groups and are particularly well optically brightened, the binder copolymers of minor amounts of monomers of the general formula in which the phenyl radicals are optionally substituted, and in which R stands for a lower, normal or secondary alkyl radical or a hydrogen atom, Y for a carbonyl or methylene group, A for an oxygen atom or an NH group, E for an oxygen atom, an NH or, in particular when p = o, N group where R1 = alkyl, n is an integer from 2 to 6 and m, o, p and q are zero and / or 1, and contain predominant amounts of other olefinically unsaturated monomers .

The binder copolymers generally contain 0.1 to 10, preferably 0.5 to 5 percent by weight of one or more A -pyrazoline compounds of the general formula given above and preferably 2 to 8 percent by weight one or more monomers with crosslinkable groups, as well as predominant amounts that Up to 99.9 total%, based on the copolymer, can be, others olefinic polymerized unsaturated monomers. With the new nonwovens, the optical Brighteners as a group of molecules, so to speak, part of the binder. He will therefore only to the same extent when washing and dry cleaning the nonwovens as the binder washed out. If the binder copolymers contain monomers polymerized with crosslinking groups, the optical brightening is The nonwovens produced with it are particularly resistant to detergents and solvents.

The phenyl radicals of the h2-pyrazolines of the formula given above can be substituted one or more times. Suitable substituents are, for example, branched and straight-chain alkyl radicals with 1 to 8 carbon atoms, aralkyl radicals, such as benzyl groups, how special Halogen atoms, such as fluorine, chlorine and bromine atoms, Carboxyl groups, carbamoyl groups, N, N-dialkylcarbamoyl groups with in general 1 to 4 carbon atoms in the alkyl radical, with alkoxycarbonyl groups in general 1 to 8 carbon atoms in the alkyl radical, also acylamino groups, acyloxy groups, Sulfo groups, aryloxysulfonyl groups, sulfonylphenyl groups, sulfamoylaryl groups, Sulfamoyl groups, N, N-dialkysulfamoyl radicals and alkoxy groups with preferably 1 to 8 carbon atoms in the alkyl radical.

Suitable # ²-pyrazlines are, for example, 1,3-diphenyl- # ²-pyrazoline-5-carboxylic acid allyl ester, 1,3-Diphenyl- # ²-pyrazoline-5-carboxylic acid vinyl ester, 1- [4-hydroxysulfonylphenyl] -3- [4-chlorophenyl] - # ²-pyrazoline-5-carboxylic acid methallyl ester, 1- [4-Carbethoxyphenyl] -3- [2,4-dimethylphenyl] -5-allyloxy- # ²-pyrazoline, 1-phenyl-3- [2,4-difluorophenyl] -vinyloxy- # ²-pyrazoline, 4-N, N-dimethylbenzamido-3-phenyl-5-acryloxymethy- # ²pyrazoline, 3- [4-chlorophenyl] -1- [4-N, N-dimethylaulfamoylphenyl] - # ²-pyrazoline-5-carboxylic acid [ß -acryloxyethyl] ester, 3- [4-Benzamido] -1- [3-n-butoxyphenyl] - # ²-pyrazoline-5-carboxylic acid - (@ - methallyloxybutyl) ester, 1-mesityl-3- [4-chlorophenyl] -5-allyloxymethyl- # - pyrazoline, 1,3-diphenyl-5-allyloxy- Lx -pyrazoline, 1- [4-chlorophenyl] -3- [4-N, N-dimethylsulfamoylphenyl] - # ²-pyrazoline-5-carboxylic acid allyl ester, 1- [2-acetylaminophenyl] -3-p-tolyl- # ²-pyrazoline-5-carboxylic acid - # - acryloylamino) propylamide, the mixed anhydride of 1,3-diphenyl- # ²-pyrazoline-5-carboxylic acid and acrylic acid and also N- [1- (4-sulfamoylphenyl) -3- (4-acetoxyphenyl) - # ²-pyrazoline-5-methyl] -N-butylallylamine. Such # 2 pyrazolines generally have a fluorescence emission maximum im Range from 400 to 460, preferably from 410 to 440 mµ.

As olefinically unsaturated monomers with crosslinkable groups can the binder copolymers are preferably acrylic and methacrylic acid amide, N-methylol amides and N-alkoxymethylamides, α ßolefinically unsaturated, preferably 3 to 6 Carboxylic acids containing carbon atoms, such as N-methylolacrylamide and methacrylamide, also N-methoxymethyl-, N-ethoxymethyl- and N-n-butoxyrietbylacryl- and methacrylamide, also olefinically unsaturated epoxy compounds, such as glycidyl methacrylate, olefinically unsaturated chlorohydrins, such as 3-chloro-2-hydroxypropyl acrylate, olefinically unsaturated Monohydroxy compounds such as 1,4-butanediol monoacrylate, ethylene glycol monoacrylate and -methacrylate, polymerized included.

Other suitable olefinically unsaturated monomers used in the binder copolymers are polymerized as the main component, especially acrylic and methacrylic acid esters from 1 to 8 carbon atoms containing alkanols, such as especially methyl acrylate, Acrylic acid ethyl ester, methyl ester, isopropyl ester, n-butyl ester and -2-ethylhexyl ester and n-butyl methacrylate and -2-ethylhexyl ester. 1,3-dienes, preferably with 1 to 6 carbon atoms, such as especially butadiene, vinyl aromatic compounds, such as especially Styrene, A-methylstyrene and chlorostyrenes, olefinically unsaturated heterocyclic ones Compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, N-acryloxypyrrolidone and N-acryloylcaprolactam, olefinically unsaturated nitriles such as acrylonitrile, methacrylonitrile, Vinyl and vinylidene halides, such as vinyl chloride, vinyl fluoride and vinylidene chloride, Vinyl esters of 1 to 18, in particular 2 to 4, carboxylic acids containing carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate, vinyl stearate, vinyl pivalate and also vinyl esters of the so-called Versatic acids.

In small amounts, which are usually between 0.5 and 10% by weight and are preferably 1 to 7 wt.%, Carboxyl-containing olefinic unsaturated monomers be polymerized into the copolymers, especially , ß-olefinically unsaturated mono- and / or dicarboxylic acids with 3 to 6 carbon atoms, such as Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and Chloroacrylic acid, and also styrene carboxylic acids.

Also monomers with several polymerizable double bonds, e.g.

1, 4-butanediol diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Formal triacrylate, diallyl phthalate, hexaallyl sorbitol and / or divinylbenzene can be polymerized in small proportions, preferably between 0.1 and 5 percent by weight, based on the copolymers. The main constituent monomers are generally chosen so that the glass temperatures of the copolymers below 500C, mostly below 200C.

The binder copolymers can be used in a conventional manner, e.g.

by copolymerization in aqueous emulsion or further in organic Solvents using the usual catalysts, regulators, emulsifiers and / or protective colloids. Suitable emulsifiers are, for example in Houben-Weyl, "Methods of Organic Chemistry", Volume XIVS1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208, described in detail. For the production of the new nonwovens, the natural ones customary for nonwovens can be used and synthetic fibers, e.g. made of cellulose, cellulose acetate, regenerated cellulose, Wool, silk, polypropylene, polyacrylonitrile, polyethylene terephthalate, polycaprolactam and / or polyhexamethyladipamide can be used.

The production of the bonded nonwovens can be carried out in a more conventional manner Way, e.g. by dipping the fleece in an aqueous binder dispersion, Squeezing and drying at elevated temperature. The binder-polymer concentration is here of the diving liquor generally between 5 and 60, mostly between 15 and 35, percent by weight. The optically brightened binders can also be used together with conventional binders and can be used with resin-forming polycondensates. One obtains, for example Nonwovens with increased crease resistance and improved feel, if one is usual Aminoplast resin precondensates in amounts of preferably 2 to 10 percent by weight used. Such precondensates can optionally be mixed with the binders react with crosslinking if the binder copolymers have co-reactive groups contain and optionally catalysts, such as acidic substances, added will. The amount of the binder copolymer, based on the amount of fiber, can be varied within wide limits. For the production of nonwovens with high porosity one uses mostly 5 to 10% total binder copolymers in dissolved or preferably in dispersed form, based on the amount of fiber. Such products are e.g. for the production of disposable items such as napkins and tablecloths, suitable. For the production of interlining nonwovens, 60 to 150 percent by weight are usually required Binder copolymer, based on the fiber weight, used. One can use such nonwovens to make dresses, blouses and shirts.

Refer to the parts and percentages given in the following examples focus on the weight. The fluorescence intensity is used to measure the lightening effect of the nonwovens obtained in UV light ("Analysis Lamp Fluortes Forte", No. 5261, Original Hanau, Quarzlampen GmbH) and with the values 0 (no lightening) Graded up to 6 (excellent brightening).

Example 1 A nonwoven made of polyhexamethylene adipamide fibers (50 g / m² basis weight, fibers 40 mm staple length, 3 den) is used with a 12 percent aqueous dispersion, one in the usual way from 365 parts of acrylic acid n-butyl ester, 44 parts of acrylonitrile, 20 parts of N-Methylo-lmethacrylamid, 9 parts of acrylic acid and 2.2 parts of 1, 3-diphenyl-A 2-pyrazoline-5-carboxylic acid allyl ester produced copolymer, impregnated and squeezed between metal rollers. It is dried at 100 ° C. and heated 10 minutes at 150 ° C and receives an optically brightened nonwoven fabric. The amount of mixed polymer, based on dlc fibers, is 34.

The optical brightening of the nonwoven has a grade of 4 and decreases if it is dry-cleaned twice in perchlorethylene at 400C it does not come off.

Example 2 The procedure described in Example 1 is followed, but used as a binder a conventionally prepared 20 percent aqueous dispersion a copolymer of 76.5 parts of ethyl acrylate, 10 parts of vinyl acetate, 2 parts of butanediol diacrylate, 2 parts of acrylic acid, 3.5 parts of 3-chloro-2-hydroxypropyl acrylic acid ester, 2 parts of N-methylolacrylamide and 4 parts of 1- (4-N, N-dimethylsulfamoylphenyl) -3- (4-chloropheny) - # ²-pyraclin-5-carboxylic acid methallyl ester, containing 2% diammonium phosphate as a catalyst. An optically brightened one is obtained Nonwoven fabric, which, based on the fibers, contains 45% binder and its optical Lightening has a grade of 4.5. The optical brightening is after two chemical cleanings unchanged with perchlorethylene at 40 ° C.

Example 3 A fleece made from 60 parts of cellulose fibers and 40 parts Polycaprolactam fibers (weight per unit area 60 g / m²) are placed between two metal sieves with a mixture of 100 parts of a 40 percent produced in the usual way aqueous dispersion of a copolymer of 50 parts of ethyl acrylate, 30 parts of 1,3-butadiene, 10 parts of acrylonitrile, 4 parts of N-methylol methacrylamide, 2 parts of acrylic acid and 4 parts of 1- (4-acetaminophenyl) -3- <4-chlorphenyl> 5-acryloxy-E 2-pyrazoline, 100 parts of water, 2 parts of a commercially available phenol-formaldehyde precondensate and 0.4 parts of ammonium oxalate impregnated, squeezed off, dried at 1200C and Annealed for 4 minutes at 1500C. The amount of binder is 100%, based on the Fibers. The nonwoven fabric obtained has an optical brightening rating of 5 to 6. It only decreases by 1/2 a note with two wet and two dry washes.

Example 4 The procedure is as indicated in Example 3, but used as a binder, a 40 percent aqueous dispersion prepared in the usual way a copolymer of 47 parts of methyl methacrylate, 40 parts of 2-ethylhexyl acrylate, 2 parts of ethylene glycol monoacrylate, 3 parts of N-methoxymethylacrylamide, 3 parts of acrylamide, 2 parts of maleic acid and 3 parts of 1- (4-benzamido) -3- (4-tolyl) - # ²pyrazoline-5-carboxylic acid (β-acryloxyethyl) ester. A nonwoven fabric is obtained, the optical brightening of which has a rating of 4 to 5. the Optical brightening decreases after washing twice with perchlorethylene at 250C not off.

EXAMPLE 5 The procedure described in Example 3 is repeated, but using as a binder a conventionally prepared 45 percent aqueous dispersion a copolymer of 61.5 parts of butyl acrylate, 20 parts of acrylonitrile, 10 parts of vinyl chloride, 5 parts of N-methylol methacrylamide, 1 part of vinyl pyrrolidone, 1 part acrylic acid and 1.5 parts 1- (4-sulfamoylphenyl) -3-phenyl- # ²-pyrazoline-5-carboxylic acid allyl ester. A nonwoven is obtained, its optical Lighten the note 4 has. It takes on wet washing at 650C or dry cleaning in perchlorethylene at 400C not abt.

Example 6 A laminate needled in the usual way is impregnated from a jute fabric with a basis weight of 200 g / m², a non-woven wool fleece with a basis weight 400 g / m² and a fleece made of polycaprolactam fibers with a basis weight of 400 g / m² with a mixture of 50 parts of a 40 percent strength prepared in the usual way aqueous dispersion of the copolymer of 70 parts of butyl acrylate, 10 parts of acrylonitrile, 6 parts of acrylic acid, 3 parts of N-methylolacrylamide, 3 parts Methacrylamide and 8 parts 1- (4-chlorophenyl) -3- (2,4,6-mesityl) -5-allyloxymethyl- A2-pyrazoline, 50 parts of a 40 percent aqueous solution prepared in a conventional manner Dispersion of the copolymer of 71 parts of n-butyl acrylate, 20 parts Acrylonitrile, 4 parts of 3-chloro-2-hydroxypropyl acrylate, 2 parts of acrylic acid and 3 parts of N-methylol methacrylamide, 150 parts of water and 2 parts of ammonium oxalate, squeezes and dries at 1600C. A textile floor covering is obtained which is 25 %, based on the fibers, contains binder copolymer and its optical Lightening has a grade of 4 to 5.

Example 7 A nonwoven made of polyhexamethylene adipamide fibers (surface weight 50 3 fibers, 40 mm staple length, 3 den) is mixed with a mixture of 50 parts of a 45 percent aqueous dispersion of a copolymer prepared in a conventional manner from 85 parts of ethyl acrylate, 5 parts of methacrylonitrile, 6 parts of 1,4-butanediol monoacrylate, 1 part of acrylamide and 3 parts of 1,3-diphenyl-2-pyrazoline-5-carboxylic acid methallyl ester, 8 parts of dimethylolglyoxalmonourein, 1.3 parts of ammonoxalate and 100 parts of water impregnated, squeezed off, dried at 1000C and heated to 1500C for 2 minutes. The amount of binder copolymer, based on the fibers, is 50%. A nonwoven fabric is obtained, the optical brightening of which has a rating of 4.

Example 8 A fleece made from 40 parts of cellulose fibers and 60 parts of polycaprolactam fibers of the basis weight / hts 55 g / m² is with a mixture of 100 parts in usual Wise prepared 40 percent aqueous dispersion of a copolymer from 80 parts of n-butyl acrylate, 14 parts of acrylonitrile, 5 parts of N-methylol methacrylamide and 1 part acrylic acid, 1 part ammonoxalate and 100 parts water impregnated, squeezed off, dried at 1200C and tempered for 5 minutes at 1600C. The binder absorption is 100%, based on the fibers.

The nonwoven fabric obtained is produced in a conventional manner with a 12 percent aqueous dispersion of a copolymer of 65 parts of vinylidene chloride, 15 parts of ethyl acrylate, 15 parts of vinyl chloride and 5 parts of 3-chlorophenyl-1- (4-N, N-dimethylsulfamoylphenyl) - # ²-pyrazoline-5-carboxylic acid allyl ester impregnated, squeezed off, dried at 1000C and calendered. The binding agent absorption, based on the fiber weight, is 18%. The obtained nonwoven fabric has the optical Brightening of grade 3. It is extremely resistant to the effects of Solvents.

Claims (1)

Claim Bound, optically brightened fiber webs based on natural and / or synthetic fibers and binder copolymers which carry optically brightening groups, characterized in that they are copolymers of minor amounts of monomers of the general formula as binders in which the phenyl radicals are optionally substituted, and in which R stands for a lower, normal or secondary alkyl radical or a hydrogen atom, Y for a carbonyl or methylene group, A for an oxygen atom or an NH group, E for an oxygen atom, an NH or NR1 group with Rl = alkyl, n for an integer from 2 to 6 and m, o, p and q for zero and / or 1, and contain predominant amounts of other olefinically unsaturated monomers.