Means for bating, fatliquoring or hydrophobic finishing of leather and fur skins
(57) Abstract:Use: for the treatment of skins and furs. The inventive skin or fur skins treated with copolymers containing 20-70 wt.% hydrophobic monomer selected from alphaolefins long-chain - alkyl/meth/acrylate long-chain vinyl esters of carboxylic acids with long-chain vinyl ethers of long-chain or mixtures of these monomers, 1-60 wt.% monomer with special polysiloxane group, and 20 to 35 wt.% water-soluble, unsaturated acids, anhydrides of unsaturated C4-C6-dicarboxylic acids, complex profirov or polamidon unsaturated C4-C6- dicarboxylic acids or mixtures of these monomers, in a partially neutralized form in the aqueous solution or dispersion. 3 C.p. f-crystals, 1 table. The invention relates to the leather industry, namely the use of special copolymers containing monomers with a polysiloxane group for processing leather and fur skins and obtaining a soft, velvety fur skins with excellent water-repellent properties. Known use as tools hair care polymers containing 0-84,9 wt. hydrophobin is this monomer contains at least one unsaturated radically curable group and one polysiloxane group of the formula
< / BR>in which a=1-150,
and 15-99,9 wt. hydrophilic ethyleneamines monomer selected from radically polymerized cationic, anionic, nonionic or amphoteric monomers. It is preferable to strengthen the hair roots add the polymer from 40-84,5 wt. hydrophobic monomer containing 0.5-70,0 wt. polysiloxane group monomer and 15-59,5 wt. hydrophilic monomer. Means of hair care products are used in quantities of from 0.1 to 10.0 wt. and used in conventional cosmetic compositions.The task of the invention is the application of known copolymers for the treatment of leather furs.Prior art also includes gidrofobizirovan skin using polysiloxanes, which is performed by using an organic solution or an aqueous emulsion. When using water emulsion required for the preparation of the emulsion, the emulsifier system is necessary to inactivate tanning additives of metal salts, that is, as mentioned, is undesirable.Regardless of the practical use of unbound polysiloxane due to their migration in the skin cause difficulties associated with the strength of adhesion of conductive devices, and difficulties embedded finishing of skins and furs about softness, neck and gidrofobizirovan using bisimulation polysiloxane copolymers, which eliminates the above disadvantages.This problem is solved by the application as a means for bating, fatliquoring and hydrophobic finishing of leather and fur skins copolymers, which contain:
(a) 20-70 wt. hydrophobic monomer selected from the group of alphaolefins with a chain length of C-atoms 12-30 containing alkyl(meth)acrylates with a chain length of C-atoms in the alkyl chain 12-30, complex, vinyl esters of carboxylic acids with a chain length of C-atoms 12-30, simple vinyl esters with a chain length of C-atoms 12-30 or mixtures of these monomers;
b) 1-60 wt. one or more monomers with a polysiloxane group of the formula
moreover the structural fragments [OSi(R1)2] and [OSiR1A] in the formula (2) should be statistically distributed along the chain and where R1denotes phenyl or methyl, R2denotes A phenyl or alkyl with the number of C-atoms of 1-30, n=2-100, z=1-3, and A represents an unsaturated, radically curable group selected from the
C) 20-35 wt. water-soluble, unsaturated polymerized containing acid groups of the monomers and/or anhydrides of unsaturated C4-C6-dicarboxylic acids and/or profirov and/or polyamides unsaturated C4-C6-dicarboxylic acids or mixtures of these monomers, provided the amounts of the components contained in the copolymer is 100% in the partially neutralized form in the aqueous solution or dispersion.With the help of these copolymers is a higher quality finish leather and furs about softness, neck and gidrofobizirovan compared with the means of fatliquoring and gidrofobizirovan known from the prior art.The copolymers obtained by radical polymerization in bulk or solution of the monomers of groups (a), (b) and (C) in the temperature range from 50 to 200oC.The corresponding monomers of group (a) are alpha-olefins with at least 12 carbon atoms, such as, for example, dodecan, tetradecene, hexadecene, octadecene, C20-olefin-1, C24-olefin-1, C30-olefin-1, or technical mixtures of different fractions with defined limits on boiling.In to the l(meth)acrylate, stearyl(meth)acrylate, oleyl(meth)acrylate, n-eicosyl(meth)acrylate, n-docosyl(meth)acrylate or esters derived from (meth)acrylic acid and technical mixtures of fatty alcohols, such as alcohols, C12-C14C14-C18or C20-C22.As monomers of group (a) can be used also vinyl esters of carboxylic acids with the number of C-atoms 12-30. Such monomers are, in particular vanillaware, vinylacetat, ministart, vinilla or vinyl esters of fatty acids of fat. Suitable for use as monomers of group (a) are, in addition, a simple vinyl esters of long-chain, as, for example, dodecylphenyl ether, tridecemlineatus ether, hexadecimally ether, octadecylsilyl ether, alarmingly ether or tetramethylenebis ether.As components of group (b) apply radically curable monomers with a polysiloxane group of the General formula (1) and/or (2):
A-Si(R1)2[OSi(R1)2]n-R2< / BR>(R1)3Si[OSi (R1)2]n[OSiR1A]zSi (R1)3< / BR>moreover the structural fragments [OSi(R1)2] and [OSiR1A] in the formula (2) doliner or alkyl with the number of C-atoms of 1-30, n=2-100, z=1-3, and A represents an unsaturated, radically curable group selected from
< / BR>where m is 0 to 10; p is 1 to 4; R3H or methyl; X is 0 or nAs examples, the following monomers (b): alpha, omega-divinyltetramethyldisiloxane, alpha, omega-divinyltetramethyldisiloxane, allyltrimethylsilane, alpha, omega-diallylbarbituric, alpha, omega-di(meth)acryloyloxyhexyloxy, alpha, omega-di(meth)acryloyloxy(2-hydroxy-3-propoxyphenyl)polydimethylsiloxane, alpha, omega-di(meth)acryl-aminopropyltrimethoxysilane, (meth)acrylamidophenylboronic, malooleksandrivka, alpha, omega-timelineofroaldamundsen, N-(2-(meth)acryloyloxy)carbamoyloximes-polydimethylsiloxane, timelineofroaldamundsen, N-(2-(meth)acryloyl-hydroxy-ethyl)carbamidomethylation, poly(dimethylsiloxane-demetilpolisiloksana), poly(dimethylsiloxane-co-methyl(meth)-acryloyloxyhexyloxy) and poly(dimethylsiloxane-with-methylaluminoxane).The monomers of group (b) selected from the listed water-soluble unsaturated monomers bearing acid groups, such as su is whether polyamide unsaturated C4-C6-dicarboxylic acids, such as (meth)acrylic acid, basis of itaconic acid, maleic acid, acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, Metallistov acid, styrelseledamot acid, maleic anhydride, anhydride basis of itaconic acid, the anhydride metromanila acid and palefire respectively polyamide maleic acid, fumaric acid, basis of itaconic acid or metromanila acid. The proposed primary and secondary amines, of which through reaction with dicarboxylic acids or with anhydrides of dicarboxylic acids get polyamide, can have from 1 to 30 C-atoms, such as methylamine, dimethylamine, Propylamine, dibutylamine, cyclohexylamine, dodecylamine, stearylamine, oleylamine, ethanolamine or propanolamine. Complex palefire get interaction dicarboxylic acids, respectively anhydrides with alcohols.Suitable for this purpose alcohols are, for example, methanol, ethanol, isopropanol, n-, i - and/or tertbutanol, cyclohexanol, octanol, dodecanol, stearyl alcohol, ocenol, beganovic alcohol or faction technical fatty alcohols, as C12-C14-alcohol or C16-Ctlaut by radical polymerization in the temperature range from 50 to 200oC, namely by radical polymerization in bulk or in solution. Preferred polymerization in mass, but in those cases, when the molar mass of the copolymers, respectively, the viscosity of the polymer mass is too high and there are difficulties in the management process, it is possible to dilute the use of the solvent. Preferred are those solvents that are used in compositions for finishing leather, as, for example, olefins/paraffins, high-boiling aromatic hydrocarbons, esters of fatty acids, triglycerides or butylglycol.The molecular weight of the copolymers is in the range from 1000 to 40,000 g/salt and it can be adjusted by selecting an appropriate temperature of polymerization, the number of initiators and under certain conditions with regulators. To initiate polymerization using a known polymerization initiators in amounts of from 0.1 to 7.0 wt. (relative to the weight of monomers) from which the expert can easily choose the most suitable catalysts needed to obtain the desired polymerization temperature.The monomers of group (b) containing "depolimerization as" copolymers, can be floor is th acid, unsaturated glycidyl connection or unsaturated isocyanate compound and a hydroxy - or amino-functional polysiloxane. These possibilities are illustrated by the following reaction equations:
< / BR>It is also possible to carry out these reactions only in those cases where the anhydride of an unsaturated dicarboxylic acids, unsaturated glycine connection or unsaturated isocyanate connection is already copolymerizable. This means that functional polysiloxane through the reactive group of the copolymer is associated with the copolymer. Also structural fragments profirov dicarboxylic acids and polyamide dicarboxylic acids of group (b) containing copolymers, can be pre-formed in the monomer; but it is also possible the formation of these structural fragments from dicarboxylic acids or anhydrides of the acids and the corresponding alcohols or amines only during the polymerization or after it.After receiving copolymers last transferred to an aqueous solution or dispersion, to produce this Supplement water and the appropriate amount of base sufficient to carry out a partial neutralization of the carboxyl groups, respectively, acid-ang 5 to 9 in an aqueous solution or dispersion. For use as a neutralizing means of suitable hydroxides of alkali metals, amines and ammonia.Thus obtained aqueous dispersion of copolymers suitable for processing all tanned conventional methods of skins and furs. Usually tanned skin before treatment is neutralized. Before or after processing can be painted copolymers.Processing tanned leather copolymers produced in water fleet, obtained by diluting dispersions of copolymers with water, at pH 4-9 and temperatures in the range from 20 to 60oC for preferably 20-90 min, for example, by processing in the drum.The number used in the form of a solid copolymer is relative to the shaved weight of the leather or weight, fur skins in the wet state, preferably 2-15 wt. The length of the bath usually 30-500% After this treatment, the pH of the water of fleet additions of acids, preferably formic acid, reduced to 3-4; then treated leather and fur skins washed with water, dried and subjected to further processing in the usual manner.Application of known substances for retanning or conventional feeding means, as, for example, on the basis of sulfat or esters of phosphoric acid, it is possible and may occur prior to the processing of the copolymers, during treatment and after it.Due to finishing copolymers of leather and fur skins get beautiful, soft and full handle, and a uniform pattern. Water-repellent properties of skins and furs become so high that there is no need for further consolidation with mineral salts.Testing of finished leather for vlagopoglascheniem and resistance exercise using the Bally penetrometer, and the number of cracks and bends using the control device meser.Obtaining dispersions of copolymers of
Getting monomer with a polysiloxane group. In a three-neck glass flask with a stirrer and cooling load of 800.0 g of alpha, omega-hydroxypropylmethylcellulose (Tegomer H-Si 2311, Th.Goldschmidt A. G), 63,0 maleic anhydride and 0.5 g of tributylamine, heated for 2 h to 120oC. the result with a quantitative yield of polyether maleic acid used dihydroxyphenylalanine.Obtaining a copolymer. In a reactor equipped with a mixer and metering device, a load of 300 g octadecene-1 and heated to 140oC, then cooled to 100oC. Next, add heated to 70oC solution of 300 g of 45% sodium hydroxide solution and 3680 g of water, stirred to obtain a homogeneous dispersion. After cooling, get a plastic paste containing 30% of active substance that can be diluted with water in any quantity. The copolymer contains a 21.5 wt. octadecene-1, to 57.0 wt. polysiloxane monomer and 21.5 wt. acrylic acid.Dispersion II
In a reactor equipped with a mixer and metering device, load 1000 g octadecene-1 and 825 g of alpha, omega-hydroxypropylmethylcellulose (Tegomer H-Si 2311, Th.Goldschmidt AG) and heated to 130oC. for 4 hours continuously add in a unit dosage form 66 g of molten maleic anhydride, 30 g of peroxide di-tertbutyl and 40 g tertBUTYLPEROXY-2-ethylhexanoate, as well as a mixture of 580 g of acrylic acid and 100 g of dodecylmercaptan. Then continue to mix for another 2 h at 150oC, after cooling to about 100ooC to obtain a homogeneous dispersion. After cooling, get a viscous dispersion containing approximately 30% of the active substance that can be diluted with water in any quantity. The copolymer contains a 40.5 wt. octadecene-1, 36,0 wt. polysiloxane monomer and 23.5 wt. acrylic acid.Dispersion III
In a reactor equipped with a mixer and dosing devices, load 700 g C20-C24-alpha-olefin mixture, and 200 g of alpha, omega-hydroxypropylmethylcellulose (Tegomer H-Si 2311, Th.Gldschmidt AG) and heat the mixture to 150oC. for 4 h in the reactor add in a unit dosage form 350 g of molten maleic anhydride and a solution of 100 g of butylglycol, 30 g of peroxide di-tertbutyl and 10 g tertBUTYLPEROXY-2-ethylhexanoate. Then continue to mix for another 2 h at 150oC, then cooled to 100oC and add 140 g of water. During the next 30 min add dosed in the form of a mixture of 380 g of 45% sodium hydroxide solution and 180 g of water, forming a homogeneous dispersion. After cooling, get a plastic paste containing 40% of active substance that can be diluted with water in any quantity. The copolymer contains about 56 wt. alpha-olefin, 17 wt. polysilk what melitele and dosing devices, download 300 g octadecene-1 and heated to 150oC. for 4 h add in a unit dosage form 250 g of molten maleic anhydride, a mixture of 300 g of sterilisability, 40 g of alpha, omega-aryloxypropanolamine (Tegomer V-Si 2550, Th. Goldschmidt AG) and 30 g of dodecylmercaptan, and the mixture B from 50 g of methyl ester of oleic acid and 20 g of peroxide ditertbutyl. Then continue stirring for another 2 h at 150oC, and then cooled to approximately 100oC add heated to 70oC solution of 272 g of 45% sodium hydroxide solution and 1760 g of water and stirred at 90oC before the formation of a homogeneous dispersion. After cooling, get a plastic paste containing 35% of active substance that can be diluted with water in any quantity. The copolymer contains 67.5 wt. hydrophobic monomers, 4.5 wt. polysiloxane monomer and 28 wt. maleic anhydride.The variance V
In a reactor equipped with a mixer and dosing devices, load 490 g C20-C24- alpha-olefin mixture and 70 g of poly(dimethylsiloxane-with-methylvinylsiloxane) with a viscosity of 1000 mPas, the content of Si-vinyl 0.2 mol. and heated to 130oC. Then through different inlet devices is g methyl ester of oleic acid, 28 g of dodecylmercaptan, and 210 g of liquid maleic anhydride. After another 1 h, during which the reaction is continued at 130oC, the mixture is cooled to 80oC, then add a mixture of 252 g of NaOH (50%) and 2280 g of softened water and continue stirring for another 1 h At the room temperature get plastic paste containing approximately 30% 1. The use of copolymers containing 20 to 70 wt. hydrophobic monomer selected from the group of alpha-olefins with a chain length of carbon atoms of 12 to 30 containing alkyl(meth)acrylates with a length of chain carbon atoms in the alkyl chain of 12 to 30, sophisticated vinyl esters of carboxylic acids with long chains of carbon atoms of 12 to 30, a simple vinyl esters with a chain length of carbon atoms of 12 to 30, or a mixture of these monomers, 1 to 60 wt. one or more monomers with a polysiloxane group of the formula
moreover the structural fragments [OSi(R')2] and [OSiR'A] in the formula II should be statistically distributed along the chain and
where R' is phenyl or methyl,
R2But, phenyl or alkyl with the number of carbon atoms of 1 to 30,
n 2 100,
CH2CH CH2X (CH2)p-,
< / BR>< / BR>< / BR>< / BR>< / BR>or
< / BR>where m is 0 to 10;
p 1 4;
R3H or CH3;
X is 0 or NH;
20 35 wt. water-soluble, unsaturated, polymerized containing acid groups of the monomers and/or anhydrides of unsaturated dicarboxylic acids with the number of carbon atoms of 4 to 6, and/or polyesters, or polyamides, unsaturated dicarboxylic acids with the number of carbon atoms of 4 to 6, or a mixture of these monomers, provided the amount of the monomer contained in the copolymer is 100% in the partially neutralized form in the aqueous solution or dispersion as a means of abating, fatliquoring or hydrophobic finishing of leather and fur skins.2. The use of the copolymer under item 1 in the amount of 2 to 15 wt. the active substance relative to the shaved weight of the leather and fur skins.3. The use of copolymers under item 1 in combination with a conventional hydrophobic means.4. The use of copolymers under item 1 in combination with a conventional fatliquors.
FIELD: leather industry.
SUBSTANCE: semifinished product is degreased, neutralized, dyed, and lubricated. Dyeing is performed in two washing-interrupted steps with anionic black dye consumed in amount 0.5-0.6% of the weight of semifinished product in each dyeing step. Lubrication is followed by retannage with chrome tanner in amount 0.6-1.0% of the weight of semifinished product (calculated for chromium oxide) and treatment with 0.8-1.0% of spindle oil.
EFFECT: achieved deep black color and high performance characteristics.
1 tbl, 5 ex