Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
  • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine

Definitions

• the invention relates to an agent for treating fiber materials which contains at least two components which have special compositions. It also relates to the use of such agents for the treatment of fiber materials.
• fiber materials which contain natural, regenerated or synthetic fibers with certain agents in order to impart certain desired properties to the materials, for example textiles.
• the fiber materials are usually in the form of fabrics such as woven fabrics, knitted fabrics or "non-wovens" (nonwovens).
• nonwovens nonwovens
• the properties that are to be imparted to the fiber materials include, among other things, a pleasantly soft feel and water and / or oil-repellent effect.
• Fluorine-containing polymers are widely used to achieve the water- and oil-repellent properties of textiles. This is described, for example, in US Pat. No. 4,742,140 or in EP-A 0 325 918.
• copolymers are used which are composed of acrylates containing perfluorinated groups, vinylidene chloride and (meth) acrylates as monomers . These copolymers can be used in the form of aqueous dispersions which contain ethoxylated fatty acids as emulsifiers. If textile fabrics are treated with dispersions of copolymers in accordance with this US patent, however, it must be noted as a disadvantage that the effectiveness of the oil and water repellency is not satisfactory in all cases. In addition, the textiles so finished do not yet have an optimally soft handle.
• the present invention was therefore based on the object to provide a means for the highly effective oil- and water-repellent finishing of fiber materials, which provides the materials equipped with a pleasantly soft handle and which, if possible, additionally ensures that it is made from colored materials have improved solvent resistance of the coloring, in particular also to solvents such as acetone, perchlorethylene and / or methyl ethyl ketone.
• the agents according to the invention give the fiber materials such as textiles equipped with them a pleasantly soft feel and very good oil and water-repellent properties. Finishing with these agents shows a very good permanence towards washing processes and against solvents.
• the aqueous dispersions of components A) and B) can be added to other agents used for textile finishing, such as antistatic agents, without the stability of the dispersions and the finishing effects, such as oil and water repellency or soft feel, being adversely affected.
• the agents according to the invention contain at least two components A) and B), each of which is an aqueous dispersion.
• the weight ratio of component A) to component B) is in the range from 30 to 70 to 70 to 30. Mixing ratios outside this range lead to less good results. The further the mixing ratio is from the range according to the invention, the more the results regarding solvent fastness approach those which are obtained with the pure components A) or B) and which are not fully satisfactory.
• Particularly preferred among the agents according to the invention are those in which the weight ratio of component A) to component B) is approximately 50 to 50. With a weight ratio of this magnitude, the synergism between A) and B) is particularly pronounced.
• Constituent a) is a copolymer which is composed of three monomers, namely a perfluoroalkylethyl acrylate or a perfluoroalkylethyl methacrylate, vinyl chloride and a fluorine-free alkyl acrylate or methacrylate.
• the perfluoroalkylethyl acrylate is 50 to 60% by weight, vinyl chloride 2 to 10% by weight and the fluorine-free alkyl (meth) acrylate 30 to 40% by weight, the sum of the weight percentages present in the individual case always being 100.
• the radical R f is preferably an unbranched radical having 4 to 10 carbon atoms. Due to cost reasons, the perfluoroalkyl ethyl acrylate is not a uniform product, but a mixture of compounds that differ in the chain length of the R f group . In at least 95% of all compounds contained in the mixture, however, the radical R f has 2 to 14 C atoms; in the majority of the individual molecules the radical R f preferably contains 4 to 10 carbon atoms.
• the fluorine-free alkyl acrylate or alkyl methacrylate contained as a monomer unit in the copolymer (component a) of component A) is an acrylic or methacrylic acid ester of an aliphatic straight-chain or branched alcohol with an alkyl chain of 10 to 18 carbon atoms.
• component a) of component A is an acrylic or methacrylic acid ester of an aliphatic straight-chain or branched alcohol with an alkyl chain of 10 to 18 carbon atoms.
• the perfluoroalkylethyl acrylates explained above, also in the case of the fluorine-free (meth) acrylate there is normally a mixture of esters which differ in the chain length of the alcohol component. In at least 95% of the individual molecules, however, there is a chain length of the alcohol component of 10 to 18 carbon atoms.
• the fluorine-free acrylate n-octadecyl acrylate contained as component in component a) is preferred.
• the copolymers which can be used as component a) of component A) can be prepared from the monomers by customary methods, e.g. by means of emulsion polymerization.
• Component b) of component A) is an ethoxylated alkphenol of the formula R-C6H4-O (CH2CH2O) p -H
• the radical R is an unbranched or branched alkyl radical with 4 to 12, preferably 6 to 10, carbon atoms, which is preferably in the p-position to the phenol oxygen.
• the value for p (degree of ethoxylation) is 6 to 20, preferably 10 to 16.
• component b) is normally also a mixture of compounds which differ in the length of the radical R and in the degree of ethoxylation. Such mixtures are commercially available products that are on the market as emulsifiers, among other things.
• the third component c) of component A) is water
• Either an aqueous dispersion B1 or an aqueous dispersion B2 is used as component B).
• Component d) is a copolymer which is composed of three monomers, namely a fluorine-containing acrylate, vinylidene chloride and a fluorine-free alkyl acrylate or alkyl methacrylate.
• the fluorine-containing acrylate is 40 to 75% by weight, vinylidene chloride 10 to 35% by weight and the fluorine-free alkyl (meth) acrylate 10 to 25% by weight, the sum of the percentages by weight always being 100.
• k can take the values 1 to 12.
• the fluorine-containing acrylate contained as a monomer unit in the copolymer (component d)) does not have to be a uniform product, but rather is normally a mixture of products which fall under the above-mentioned formula and differ in the chain length of the fluorinated radical, ie in the value of distinguish k.
• Fluorine-containing acrylates of the formula mentioned are particularly preferred for the agents according to the invention, in which in 0 to 10% of the monomers k has a value of 4 or less has a value of 6 in 45 to 75% of the monomers k has a value of 8 in 20 to 40% of the monomers k has a value of 10 in 1 to 20% of the monomers k in 0 to 5% of the monomers k has a value of 12.
• fluorine-containing acrylates it also applies to the fluorine-free alkyl (meth) acrylates that a mixture of compounds which differ in the chain length of the alkyl radical is normally present as the monomer unit. In any case, however, these are compounds whose alkyl chain has 2 to 18 carbon atoms. These alkyl chains can be branched or unbranched.
• Copolymers which (as component d) of component B1) are suitable for the preparation of agents according to the invention are described in US Pat. No. 4,742,140. Methods for the production of such copolymers are also given there, for example by means of emulsion polymerization.
• Ingredient e) is a mixture of ethoxylated fatty acids, which can be obtained in a known manner by reacting a mixture of fatty acids with ethylene oxide. Since a mixture of fatty acids of different chain lengths is normally used in the synthesis for cost reasons, the products obtained are a mixture of compounds which differ in the chain length of the fatty acid residues and in the degree of ethoxylation. Mixtures of compounds whose fatty acid residues have 8 to 18, preferably 12 to 18 C atoms and whose degree of ethoxylation is 6 to 20, preferably 10 to 16, are used for the agents according to the invention. The degree of ethoxylation is the average number of -CH2-CH2-O units attached to a fatty acid residue. Component e) acts as a dispersant for component d) Component f) of component B1) is water.
• component B2) explained below can also be used.
• Component B2) is an aqueous dispersion which contains at least the components g) to k) described below in the following amounts: Component g): 2 to 10 parts by weight Component h): 10 to 40 parts by weight Component i): 0.5 to 10 parts by weight Component k): 40 to 90 parts by weight
• Component g) is an isocyanate which is blocked by means of an oxime.
• This means that the -NCO groups of the underlying isocyanate were blocked by reacting the isocyanate with an oxime R1 R2 C NOH, where R1 and R2 are normally alkyl radicals with 1 to 4 carbon atoms.
• Suitable as the underlying isocyanates are, for example, 2.2.4- or 2.4.4-trimethylhexamethylene diisocyanate or a mixture of these isomers.
• a suitable blocked isocyanate is Desmodul® L 75 (Bayer AG, DE). Further suitable blocked isocyanates are described in EP-196 309.
• the products obtainable in this way are distinguished by the fact that high effectiveness with regard to oil and water repellency is achieved when textiles are equipped with compositions which contain these products.
• Component i) of component B2) is an ethoxylated fatty amine or the salt which is formed from such a fatty amine and an aliphatic monocarboxylic acid having 1 to 4 carbon atoms. Suitable salts are described below in the section on component D). The same salts as for component D) are suitable for component i) of component B2), but also the underlying ethoxylated fatty amines which are not neutralized with carboxylic acid.
• Component k) of component B2) is water
• component B1) or B2) of the agents according to the invention also contains one or two further constituents I) and / or m, and moreover no further constituents.
• the components I) and m) are 5 to 10 parts by weight of acetone or 2 to 6 parts by weight of ethylene glycol or 1,2-popanediol. These values for the parts by weight relate to the above-mentioned numbers for the parts by weight of the components d), e), f), or g), h), i), k).
• a further constituent (s)) is preferably also present in component A), namely acetone in an amount of 10 to 15 parts by weight, based on the above values for parts by weight of the constituents a), b), and c),.
• Component A) preferably contains no further constituents apart from a), b), c) and, if appropriate, n).
• the agents according to the invention can be prepared by combining the two aqueous dispersions (components A) and B)) and used in this form. In certain cases, however, it is advantageous to add other products to the combined dispersions. In this way, the fiber materials treated with agents according to the invention can be given even more special properties. In particular, textile fiber materials can be conveyed even more comfortably if the agents according to the invention contain, in addition to components A) and B), a component C) and / or a component D). Above all, the simultaneous presence of components C) and D) leads to very good effects.
• the polysiloxane in component C) is a polydimethylsiloxane in which a part, usually less than 25%, of the Si-CH3 bonds has been replaced by Si-H bonds.
• Such polysiloxanes are commercially available products. All corresponding polysiloxanes available on the market can be used for the agents according to the invention, provided the stability of the aqueous dispersions containing them corresponds to the respective requirements.
• the ethoxylated alcohol contained in component C) has a degree of ethoxylation (average number of CH2CH2O units) of 4 to 12, preferably 6 to 8.
• the underlying alcohol is an aliphatic alcohol with an unbranched or branched alkyl chain of 6 to 16, preferably 10 to 12, carbon atoms.
• the third component of component C) is water.
• Component C) contains 30 to 40 parts by weight of the polysiloxane, 1 to 5 parts by weight of the ethoxylated alcohol and 60 to 65 parts by weight of water.
• Component D) is also a mixture in the form of an aqueous dispersion.
• This mixture contains a tetrasubstituted urea, a carboxylic acid salt of a fatty amine ethoxylate, ethoxylated ricinoleic acid and water.
• smaller amounts, ie in each case up to 5 parts by weight (based on the weight data given below for component D), of one or more of the following substances in component D) may be present: Ethylene glycol, methanol, acetic acid and isobutanol. The sum of all available amounts of these substances is therefore a maximum of 20 parts by weight.
• Component D) contains 15 to 25 parts by weight of the tetrasubstituted urea 1 to 2 parts by weight of the carboxylic acid salt mentioned 1 to 2 parts by weight of ethoxylated ricinoleic acid 60 to 75 parts by weight of water and optionally additionally one or more of the substances mentioned above.
• the tetrasubstituted urea is a compound of the formula wherein R is an alkyl radical having 12 to 18 carbon atoms, R ', R "and R"''independently of one another represent hydrogen or a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.
• This urea can also be a mixture of compounds which differ in the chain lengths of one or more radicals R, R ', R'',R''.
• the carboxylic acid salt of a fatty amine ethoxylate contained in component D) can be obtained by ethoxylating a fatty amine and reacting the ethoxylation product with an equivalent amount of a carboxylic acid.
• the salt preferably has the formula R4-NH (R6) +- (CH2 CH2 O) y -H + R5 COO ⁇ in which R4 is an alkyl radical having 10 to 18 carbon atoms, R5 is an alkyl radical having 1 to 4 carbon atoms, R6 is hydrogen or (CH2CH2O) y and y has values from 2 to 16.
• the salt in this case is normally a mixture of salts which differ in the chain length of the radicals R4, R5 and / or in the value of y.
• the radicals R4 and R5 can be branched, but are preferably unbranched.
• the ethoxylated ricinoleic acid contained in component D) has a degree of ethoxylation of 2 to 12.
• degree of ethoxylation of 2 to 12.
• the agents according to the invention preferably contain components A) to D) weight ratio 40 to 50% A 40 to 50% B 0 to 10% C 0 to 10% D.
• the agents according to the invention are aqueous dispersions which are outstandingly suitable for the water- and oil-repellent finishing of fiber materials, in particular textile fabrics, and which impart good color fastness to solvents and a pleasantly soft feel.
• the textile fabrics are preferably those which consist of cellulose fibers, for example cotton, or which contain cellulose fibers in a mixture with other fibers such as polyester fibers.
• the agents can be applied in known amounts for textile finishing using known methods, such as, for example, using a padder.
• the quantitative ratio in fleet 1 was chosen so that the products a and b mentioned here (components A) and B1) of claim 1) were used in approximately the same weight ratios, the sum of a and b being approximately 90% by weight. % of the 20% aqueous dispersion formed, and the components c) and d) each only amounts of less than 10%.
• Fleet 2 (comparison, not according to the invention): The fleet contained in 1 liter of water: 1 ml of 60% acetic acid 25 g of product a, from fleet 1 (products b, c, and d, from fleet 1 were not present)
• Fleet 3 (comparison, not according to the invention): Composition like fleet 2, but with product b, from fleet 1 (instead of product a,)
• Fleet 4 (comparison, not according to the invention): Like fleet 3, but instead of product b, another commercially available dispersion, but with a similar composition to product b,
• Fleet 5 (not according to the invention): Like fleet 3, but instead of product b, the commercial product Scotchgard® FX 3563 Fleet 6 (according to the invention): Composition like fleet 1, but without the addition of products c) and d)
• a composition according to component B2) of claim 1 was used as product e.
• the product e was an aqueous dispersion which contained approximately (in% by weight) 73% water, 3% 1,2-propanediol, 2% of an acetate of a fatty amine ethoxylate (Marlowet® 5401) 7% of an isocyanate blocked with butanone oxime (Desmodur® L 75) and 15% of a urethane with perfluoroalkyl groups (corresponding to component h) of component B2).
• the solvents used for the test were acetone (Ac), perchlorethylene (Pe) and methyl ethyl ketone (Me).

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

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• 1990
  • 1990-12-19 DE DE4040641A patent/DE4040641A1/de not_active Withdrawn
• 1991
  • 1991-12-06 AT AT91120940T patent/ATE118835T1/de not_active IP Right Cessation
  • 1991-12-06 EP EP91120940A patent/EP0491248B1/fr not_active Expired - Lifetime
  • 1991-12-06 DE DE59104698T patent/DE59104698D1/de not_active Expired - Fee Related
  • 1991-12-17 US US07/809,684 patent/US5324763A/en not_active Expired - Fee Related
  • 1991-12-18 JP JP3335132A patent/JPH04289275A/ja not_active Withdrawn

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