EP1707665A1 - Process for flame-proofing of fibrous materials - Google Patents
Process for flame-proofing of fibrous materials Download PDFInfo
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- EP1707665A1 EP1707665A1 EP05006920A EP05006920A EP1707665A1 EP 1707665 A1 EP1707665 A1 EP 1707665A1 EP 05006920 A EP05006920 A EP 05006920A EP 05006920 A EP05006920 A EP 05006920A EP 1707665 A1 EP1707665 A1 EP 1707665A1
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- 239000002657 fibrous material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 17
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 20
- 239000003063 flame retardant Substances 0.000 claims description 20
- 210000002268 wool Anatomy 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000003009 phosphonic acids Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 240000002129 Malva sylvestris Species 0.000 description 4
- 235000006770 Malva sylvestris Nutrition 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000013351 cheese Nutrition 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000569 multi-angle light scattering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- TWMSGHOMFJVKPA-UHFFFAOYSA-N bis(2-tert-butylphenyl) hydrogen phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)(=O)OC1=CC=CC=C1C(C)(C)C TWMSGHOMFJVKPA-UHFFFAOYSA-N 0.000 description 1
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007383 open-end spinning Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007378 ring spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
-
- 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
- D06M15/61—Polyamines polyimines
Definitions
- the invention relates to a process for the flame-retardant finishing of fiber materials.
- the object has been achieved by a process for the flame-retardant finishing of a fibrous material which is in the form of a textile fabric or in the form of a yarn and contains less than 20% by weight of cellulose fibers, whereby the fibrous material is treated successively or simultaneously with a component A and a component B.
- component A is a branched polyethylenimine containing primary, secondary and tertiary amino groups and having a weight average molecular weight in the range of 5,000 to 1,500,000, preferably 10,000 to 1,000,000, and in which the ratio of secondary amino groups to primary amino groups in the Range from 1.00: 1 to 2.50: 1 and the numerical ratio of secondary amino groups to tertiary amino groups ranges from 1.20: 1 to 2.00: 1, or wherein component A is a mixture of such polyethyleninimes, wherein component B is a phosphonic acid of formula (I), (II) or formula (III) wherein in the formulas (I), (II) or (III) in up to 50% of the phosphorus bound OH groups, the hydrogen atom may be substituted by an alkali metal or an ammonium group, but preferably 100% of these OH groups in non neutralized form, or wherein component B is a mixture of compounds selected from compounds of formula (I), (II) or (III), in which y can
- fiber materials are understood as meaning yarns of natural or synthetic fibers or textile fabrics of such fibers, although mixtures of such fibers may be present. These materials are preferably free of cellulosic fibers, but in any case contain less than 20% by weight of cellulosic fibers.
- the fiber materials preferably consist of 30 to 100% by weight of wool. The remaining 0 to 70% by weight may be polyolefin fibers, polyacrylonitrile fibers, polyamide fibers. Less preferred as a mixing partner for the wool are polyester fibers.
- the fiber materials can Also, but less preferred, have a wool content of less than 30% by weight or be completely free of wool. As fibers for this alternative turn the above-mentioned fibers in question.
- a fiber material is treated successively or simultaneously with a component A and a component B. It is therefore possible for A and B to be applied simultaneously to the fiber material, for example in the form of a mixture containing components A and B. It is often advantageous to apply the components A and B in succession, and it is further preferred to apply the component A (polyethyleneimine) earlier to the fiber material than component B (phosphonic acid). It has been found that in many cases with this approach, a more effective flame retardant effect can be achieved than with the other mentioned process variants.
- component A and / or component B are not applied in a pure form to the fiber material, but in the form of a mixture with water, that is, if both component A and component B are applied in the form of a mixture which contains component A or component B and additionally water.
- component A can be used in the form of a mixture containing 50 to 500 parts by weight of water per 100 parts by weight of component A
- component B in the form of a mixture containing 20 to 300 parts by weight of water per 100 parts by weight Component B contains.
- One or both of these mixtures may contain other components, for example polymaleic acid or partially hydrolyzed polymaleic anhydride.
- the addition of partially or fully hydrolyzed polymaleic anhydride is, if such an additive is used, preferably in the range of 1 to 5% by weight, based on total mixture containing component A or component B and water.
- polymaleic acid or partially hydrolyzed polymaleic anhydride When polymaleic acid or partially hydrolyzed polymaleic anhydride is used, it is preferably added to a mixture containing component A and water. This addition causes, in a number of cases, an increase in the permanence of the flame retardant effect.
- “permanence” is meant in this context that the flame retardant properties of the fiber materials are generally retained, even when the fiber material comes in contact with water. This increase in permanence could be due to the fact that the additional use of partially or completely hydrolyzed polymaleic anhydride leads to a better fixation of the component A and / or component B on the fiber material.
- a partial ester of orthophosphoric acid to the fiber material.
- the application of this partial ester can be carried out simultaneously with the application of component A or component B or, what is preferred, separately therefrom in a separate operation.
- the amount of orthophosphoric acid partial ester which is applied is preferably in the range of 2 to 10% by weight, based on anhydrous fiber material.
- Suitable phosphoric acid partial esters include monoesters or diesters of orthophosphoric acid having 6 to 12 carbon atoms in the alcohol component of the ester, or mixtures of such mono- and diesters.
- An example of this is diisooctyl phosphate or diphenyl phosphate or bis (t-butyl-phenyl) phosphate.
- the addition of such esters can often increase the flame retardant effect.
- neither component A nor component B nor the mixtures of component A or component B and water contain metals or metal compounds, apart from immaterial impurities.
- This is an advantage for cost and environmental reasons, e.g. compared to the well-known ZIRPRO® process, where zirconium compounds are used, and also prevents the finished fiber materials from being colored by metal ions.
- component B up to 50% of the phosphorus-bonded hydroxy groups may be replaced by alkali metal or ammonium ions, hydrogen atoms are not preferred.
- the application of component A, component B or of a mixture which contains water other than component A or component B, on the fiber material can be carried out by any desired methods. It is best to apply to the fiber material a mixture containing water and component A and then a mixture containing water and component B.
- the application can, if the fibrous material is present as a textile fabric, take place by means of the known method of padding.
- the fiber material is in the form of a yarn, the application of components A and B can be carried out by passing the yarn through one or more baths containing component A or component B and water, and then drying the yarns. But it is also possible to use a coil on which the yarn is wound, dipping in a dyeing process in one or more baths containing component A and / or component B, and then to dry the coil.
- a preferred embodiment of the method according to the invention is that the weight ratio of the applied to the fiber material amount of component A to the amount of applied component B ranges from 1: 1.8 to 1: 5.0, each based on anhydrous products. Preferably, the ratio is in the range of 1: 2.3 to 1: 3.5.
- the amount of component A and component B, which are applied to the fiber material is preferably such that on the finished fiber material 3 to 10% by weight of component A and 7 to 20% by weight of component B, based on anhydrous fiber material.
- Component A is a polyethyleneimine. As is customary with polymers, this is normally not a product which consists of all the same molecules, but is a mixture of products of different chain lengths.
- polyethyleneimines the fact known from the literature is added that under normal conditions there is a mixture of branched polymers whose individual molecules also differ in the number of branching units. This is expressed by the ratio of the number of secondary to primary amino groups as detailed below and to tertiary amino groups.
- Polyethyleneimines are products known from the literature. They can be prepared inter alia by reacting 1,2-ethylenediamine with 1,2-dichloroethane.
- polyethyleneimines which can be prepared by polymerization of unsubstituted aziridine (ethyleneimine). This polymerization can be carried out by known methods, if appropriate with addition of acidic catalysts, for example hydrochloric acid, and optionally in the presence of water.
- acidic catalysts for example hydrochloric acid
- Polyethyleneimines suitable for the process according to the invention are available on the market, for example from BASF, Germany (LUPASOL® grades and POLYMIN® grades).
- the US Pat. No. 6,451,961 B2 , and the US 5,977,293 describe polyethyleneimines and processes for their preparation.
- the polyethyleneimines described there can be used for carrying out the process according to the invention, provided they meet the conditions mentioned above and in claim 1. Further describe DA Tomalia et al in "Encyclopedia of Polymer Science and Engineering, Vol. 1. Wiley NY 1985, pp. 680-739 , suitable polyethyleneimines and process for their preparation. Polyethyleneimines, their preparation and properties are also used in D. Horn. Polyethlyenimine Physicochemical Properties and Applications, in "Polymeric Amines and Ammonium Salts.” Goethals EJ, Pergamon Press: Oxford, New York 1980, pp. 333-355 , described.
- the polyethyleneimines suitable as component A for the process according to the invention are branched. That is, the polymer having end groups of formula H 2 N-CH 2 -CH 2 - and within the polymer chain, units of the formula -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH- additionally has units of the formula within the chain contains.
- the polymer thus contains primary, secondary and tertiary amino groups.
- the numerical ratios between the individual amino groups must assume values in a certain range.
- the ratio of the number of secondary amino groups to the number of primary amino groups must be in the range of 1.00: 1 to 2.50: 1, and the ratio of the number of secondary amino groups to the number of tertiary amino groups in the range of 1.20: 1 to 2.00: 1.
- the values for the numerical ratios of the various amino groups present in a particular polyethyleneimine or mixture of polyethylenimines can be determined by 13 C-NMR spectroscopy. This is explained in " T. St. Pierre and M. Geckle, 13 C-NMR Analsy is Branched Polyethyleneimine, J. Macromol. SCI.-CHEM., Vol. A 22 (5 - 7), pages 877-887 (1985 ) ".
- a preferred embodiment of the method according to the invention is that component A a Polyethyleneimine formed by polymerization of ethyleneimine and having the following structure (formula (V)) wherein the polymerization is optionally catalysed acid, wherein the individual units which contain tertiary amino groups and the individual units which contain secondary amino groups can be distributed as desired over the polymer chain, in which b is greater than a and wherein a and b have such values that the conditions mentioned in claim 1 for the molecular weight and for the numerical ratios of the amino groups with one another are met or wherein component A is a mixture of such polyethyleneimines.
- component A is normally a mixture of polyethylenimines.
- component A being a mixture of compounds of the formula (V).
- the values of a and b in the compounds of the formula (V) must, of course, be chosen so that the values for the ratios of the individual amino groups to one another and for the average molecular weight determined in the mixture are in the ranges stated above and in claim 1 ,
- the control of these values can, as mentioned, be done via the parameters in the production of the polyethyleneimines.
- Component B is a phosphonic acid of the formula (1), the formula (II) or the formula (III)
- Component B may also be a mixture of compounds selected from compounds of formula (I), formula (II) and formula (III).
- R represents a linear or branched alkyl radical. This alkyl group contains 1 to 7 carbon atoms in the case that the below-mentioned R 1 is a hydroxy group. If R 1 is hydrogen, the radical R contains 3 to 7 carbon atoms.
- the radical R 1 in formula (1) is H or OH.
- the radical R 2 is the radical
- y can take the values 0, 1 or 2.
- y has the value 0, which analogously to the case described above results in an increase in the phosphorus content on the fiber product.
- All radicals R 4 present in compounds of the formula (III) independently of one another represent hydrogen or or for a radical of the formula (IV) In this formula (IV), t is 0 or a number from 1 to 10.
- 50 to 100% of all radicals R 4 present are
- Phosphonic acids of formulas (I), (II) and (III) are commercially available products, e.g. Masquol P 210-1 from Protex-Extrosa or Briquest 301-50 A from Rhodia or the products Cublen D50 (from Zschimmer & Schwarz, DE), or Diquest 2060 S (from Solutia, Belgium). Phosphonic acids of the formulas (I), (II) and (III) can be prepared by methods generally known from the literature.
- a particularly advantageous embodiment of the process according to the invention is characterized in that component B is a mixture of phosphonic acids of the formula (II) and of the formula (III), both of which are in completely unneutralized form.
- the mixing ratio of phosphonic acid of the formula (II) and phosphonic acid of the formula (III) may assume any values.
- the weight ratio of the two types of phosphonic acid can assume values of 0: 100 to 100: 0.
- component B a compound of formula (I) or a mixture of compounds of formula (I) or a compound of formula (II) or a mixture of compounds of formula (II) or a compound of formula (III) or Mixture of compounds of formula (III) can be used. Particularly good results can be obtained if component B consists to 100% of a compound of formula (II) or a mixture of compounds of formula (II), in which case y in formula (II) has the value 0 or 1.
- the fiber materials which are treated by the process according to the invention are in the form of a textile fabric or in the form of a yarn.
- the yarn may consist of continuous filaments or may have been made of staple fibers by ring spinning or open-end spinning.
- Textile fabrics are wovens, knits or fleeces (nonwovens).
- tissues are used for carrying out the method according to the invention.
- the fiber materials preferably contain from 30 to 100% by weight of wool. Fabrics consisting of 100% wool are particularly well suited to the process of the invention. The origin of the wool is not decisive, but the quality of the wool naturally influences the properties of the final article.
- the fiber materials treated by the process of the invention can be used to make consumer textiles, such as e.g. Car seats, curtains, carpets, etc.
- mixture 1a 4.8 kg of a commercially available aqueous solution (LUPASOL® P, BASF, DE) containing 50% by weight of water and 50% by weight of polyethylenimine were mixed with 4.8 kg of water and 0.35 kg of a 50% aqueous solution of hydrolyzed polymaleic anhydride.
- the finished mixture hereinafter referred to as "mixture 1a" thus contained about 24% by weight of component A.
- This example relates to the treatment of fiber materials which are in the form of yarns with components A and B.
- Mixture 1c contained 50% by weight of mixture 1 a (according to Example 1 a) and 50% by weight of water. Mixture 1c thus contained component A. The amount of mixture 1c added was 12% by weight, based on the weight of the respective yarn, ie based on the weight of yarn 2a or 2b or 2c in all 3 tests. In all 3 experiments, the cheeses were exposed in the dyeing apparatus at room temperature for 10 minutes to the action of mixture 1 c. Subsequently, the apparatus was rinsed with water for 5 minutes and the rinse water was removed. The mixture was then added to the apparatus at room temperature for 1 d. Mixture 1 d contained 50% by weight of the mixture 1 b prepared according to Example 1b) and 50% by weight of water. Thus, mixture contained 1 d component B).
- the cheeses were exposed to the action of mixture 1d for 10 minutes at room temperature. Subsequently, the apparatus was rinsed twice each with room temperature water. The cheeses were thereupon in all attempts removed from the apparatus and dried at 120 ° C for 15 minutes. Subsequently, 1 sample of knit fabric was made from the respective yarns.
- Example 2 All 3 experiments of Example 2 were repeated with the only difference that the amount of mixture 1 c and mixture 1 d, which was added to the dyeing machine, not 12 wt%, based on yarn weight, but only 6 wt%.
- This example relates to the treatment of tissues by the method of the invention.
- the fabric used was 100% wool, dyed red, 205 g / m 2 .
- the material was treated via padding with a liquor prepared as follows:
- Example 4 was repeated, with the difference that not 45 g of the aqueous phosphonic acid solution were used, but only 30 g, and that was not dried at 150 ° C, but at 110 ° C. The solids coverage was 8.6%.
- Example 4 was repeated with the only difference that not a fabric of 100% wool was used, but a fabric of 90 wt% wool and 10 wt% polyamide.
- the burn time is the time in seconds that the pattern in question still burns after being exposed to a flame for 3 seconds and then that flame is removed. A higher value for BZ thus means worse flame retardant properties.
- the burning time was determined according to DIN 54336 (November 1986 issue). The firing times were determined both on the tissue samples obtained immediately after the mentioned drying and on the samples of the same origin, which were still washed after drying (pure water at 40 ° C./20 minutes).
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur flammhemmenden Ausrüstung von Fasermaterialien.The invention relates to a process for the flame-retardant finishing of fiber materials.
Es ist bekannt, Fasermaterialien mit bestimmten Produkten zu behandeln, um ihnen flammhemmende Eigenschaften zu verleihen. So beschreiben beispielsweise die
Die
Die aus dem Stand der Technik bekannten Verfahren zur Behandlung von Fasermaterialien sind nicht optimal, wenn es darum geht, Wolle enthaltende Materialien flammhemmend auszurüsten. Vielfach lässt sich hierbei mit bekannten Verfahren eine genügende flammhemmende Ausrüstung nicht erzielen und/oder die resultierenden flammhemmenden Eigenschaften werden bereits nach kurzer Zeit verschlechtert, wenn die behandelten Fasermaterialien mit Wasser in Berührung kommen.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein verbessertes Verfahren zu entwickeln, um Fasermaterialien flammhemmend auszurüsten, wobei insbesondere auch Fasermaterialien, die 30 bis 100 Gew% Wolle enthalten, gute flammhemmende Wirkungen verliehen werden können, die auch eine gute Permanenz aufweisen, d.h. flammhemmende Wirkungen, die nicht deutlich verschlechtert werden, wenn die Fasermaterialien mit Wasser in Berührung kommen.It is known to treat fiber materials with certain products to give them flame retardant properties. For example, describe the
The
The known from the prior art methods for the treatment of fiber materials are not optimal when it comes to equip wool-containing materials flame retardant. In many cases, sufficient flame-retardant finish can not be achieved with known processes and / or the resulting flame-retardant properties are already degraded after a short time, when the treated fiber materials come into contact with water.
It is an object of the present invention to develop an improved process for flame-retarding fiber materials, in which fiber materials containing 30 to 100% by weight of wool in particular can be given good flame-retardant effects which also have good permanence, ie flame retardant effects which are not significantly deteriorated when the fiber materials come in contact with water.
Die Aufgabe wurde gelöst durch ein Verfahren zur flammhemmenden Ausrüstung eines Fasermaterials, welches in Form eines textilen Flächengebildes oder in Form eines Garns vorliegt und weniger als 20 Gew% Cellulosefasern enthält, wobei man das Fasermaterial nacheinander oder gleichzeitig mit einer Komponente A und einer Komponente B behandelt, wobei Komponente A ein verzweigtes Polyethylenimin ist, das primäre, sekundäre und tertiäre Aminogruppen enthält und das ein Gewichtsmittel des Molgewichts im Bereich von 5.000 bis 1.500.000, vorzugsweise 10.000 bis 1.000.000, besitzt und bei dem das zahlenmäßige Verhältnis von sekundären Aminogruppen zu primären Aminogruppen im Bereich von 1,00 : 1 bis 2,50 : 1 und das zahlenmäßige Verhältnis von sekundären Aminogruppen zu tertiären Aminogruppen im Bereich von 1,20 : 1 bis 2,00 : 1 liegt,
oder wobei Komponente A ein Gemisch solcher Polyethyleninime ist,
wobei Komponente B eine Phosphonsäure der Formel (I), (II) oder der Formel (III) ist
oder wobei Komponente B ein Gemisch von Verbindungen ist, die aus Verbindungen der Formel (I), (II) oder (III) ausgewählt sind,
wobei
y die Werte 0, 1 oder 2 annehmen kann und vorzugsweise den Wert 0 besitzt,
R1 für H oder OH steht,
R für einen linearen oder verzweigten Alkylrest steht, der 1 bis 7 Kohlenstoffatome enthält, wenn R1 = OH ist und 3 bis 7 Kohlenstoffatome enthält, wenn R1 = H ist
wobei
R2 für
wobei R3 für H oder R2, vorzugsweise für R2 steht und wobei
alle Reste R4 unabhängig voneinander für H oder für
wobei t 0 oder eine Zahl von 1 bis 10 ist.The object has been achieved by a process for the flame-retardant finishing of a fibrous material which is in the form of a textile fabric or in the form of a yarn and contains less than 20% by weight of cellulose fibers, whereby the fibrous material is treated successively or simultaneously with a component A and a component B. , where component A is a branched polyethylenimine containing primary, secondary and tertiary amino groups and having a weight average molecular weight in the range of 5,000 to 1,500,000, preferably 10,000 to 1,000,000, and in which the ratio of secondary amino groups to primary amino groups in the Range from 1.00: 1 to 2.50: 1 and the numerical ratio of secondary amino groups to tertiary amino groups ranges from 1.20: 1 to 2.00: 1,
or wherein component A is a mixture of such polyethyleninimes,
wherein component B is a phosphonic acid of formula (I), (II) or formula (III)
or wherein component B is a mixture of compounds selected from compounds of formula (I), (II) or (III),
in which
y can assume the values 0, 1 or 2 and preferably has the value 0,
R 1 is H or OH,
R is a linear or branched alkyl radical containing 1 to 7 carbon atoms when R 1 = OH and containing 3 to 7 carbon atoms when R 1 = H
in which
R 2 for
wherein R 3 is H or R 2 , preferably R 2 and wherein
all radicals R 4 independently of one another for H or for
where t is 0 or a number from 1 to 10.
Im Rahmen der hier beschriebenen Erfindung werden unter Fasermaterialien Garne aus natürlichen oder synthetischen Fasern oder textile Flächengebilde aus solchen Fasern verstanden,
wobei auch Mischungen solcher Fasern vorliegen können. Diese Materialien sind vorzugsweise frei von Cellulosefasern, auf jeden Fall aber enthalten sie weniger als 20 Gew% an Cellulosefasern.
Vorzugsweise bestehen die Fasermaterialien zu 30 bis 100 Gew% aus Wolle. Die restlichen 0 bis 70 Gew% können Polyolefinfasern, Polyacrylnitrilfasern, Polyamidfasem sein. Weniger bevorzugt als Mischungspartner für die Wolle sind Polyesterfasern. Die Fasermaterialien können auch, was aber weniger bevorzugt ist, einen Wollegehalt von weniger als 30 Gew% aufweisen oder vollständig frei von Wolle sein. Als Fasern kommen für diese Alternative wiederum die oben genannten Fasern in Frage.In the context of the invention described here, fiber materials are understood as meaning yarns of natural or synthetic fibers or textile fabrics of such fibers,
although mixtures of such fibers may be present. These materials are preferably free of cellulosic fibers, but in any case contain less than 20% by weight of cellulosic fibers.
The fiber materials preferably consist of 30 to 100% by weight of wool. The remaining 0 to 70% by weight may be polyolefin fibers, polyacrylonitrile fibers, polyamide fibers. Less preferred as a mixing partner for the wool are polyester fibers. The fiber materials can Also, but less preferred, have a wool content of less than 30% by weight or be completely free of wool. As fibers for this alternative turn the above-mentioned fibers in question.
Bei dem erfindungsgemäßen Verfahren wird ein Fasermaterial nacheinander oder gleichzeitig mit einer Komponente A und einer Komponente B behandelt. Es können also A und B gleichzeitig auf das Fasermaterial aufgebracht werden, z.B. in Form eines Gemischs, das die Komponenten A und B enthält. Vorteilhaft ist es häufig, die Komponenten A und B nacheinander aufzubringen, wobei es ferner bevorzugt ist, die Komponente A (Polyethylenimin) früher auf das Fasermaterial aufzubringen als Komponente B (Phosphonsäure). Es hat sich nämlich herausgestellt, dass in vielen Fällen mit dieser Vorgehensweise eine effektivere flammhemmende Wirkung erzielt werden kann als mit den anderen genannten Verfahrensvarianten.
Entscheidet man sich dafür, die Komponenten A und B vor dem Aufbringen auf das Fasermaterial zu mischen, d.h. also A und B gleichzeitig auf das Fasermaterial aufzubringen, was vor allem in Frage kommt, wenn das Fasermaterial zu einem hohen Anteil aus Wolle besteht, so empfiehlt es sich häufig, den pH-Wert der Mischung vor dem Aufbringen auf das Fasermaterial auf einen Wert von mehr als 4, bevorzugt auf einen Wert im Bereich von 6 bis 8 einzustellen. Besonders gut geeignet für diese pH-Steuerung ist eine wässrige Lösung von Ammoniak. Es können hierzu auch Amine verwendet werden. Bei Verwendung von Ammoniak lässt sich ein Gemisch aus Komponente A, Komponente B und Wasser als homogene wässrige Lösung erhalten, die zur Behandlung der Fasermaterialien nach dem erfindungsgemäßen Verfahren sehr gut geeignet ist.
Die Verwendung von Ammoniak hat den Vorteil, dass bei einer späteren thermischen Behandlung der Fasermaterialien, z.B. bei 110°C bis 180°C, Ammoniak vom Fasermaterial entfernt wird. Die Folge ist eine gute Permanenz der flammhemmenden Ausrüstung.In the method according to the invention, a fiber material is treated successively or simultaneously with a component A and a component B. It is therefore possible for A and B to be applied simultaneously to the fiber material, for example in the form of a mixture containing components A and B. It is often advantageous to apply the components A and B in succession, and it is further preferred to apply the component A (polyethyleneimine) earlier to the fiber material than component B (phosphonic acid). It has been found that in many cases with this approach, a more effective flame retardant effect can be achieved than with the other mentioned process variants.
If it is decided to mix the components A and B prior to application to the fiber material, ie, to apply A and B simultaneously on the fiber material, which is especially in question when the fiber material consists of a high proportion of wool, so recommends It is often the pH of the mixture before application to the fiber material to a value of more than 4, preferably to a value in the range of 6 to 8 set. Particularly suitable for this pH control is an aqueous solution of ammonia. Amines can also be used for this purpose. When ammonia is used, a mixture of component A, component B and water can be obtained as a homogeneous aqueous solution which is very well suited for the treatment of the fiber materials by the process according to the invention.
The use of ammonia has the advantage that in a later thermal treatment of the fiber materials, for example at 110 ° C to 180 ° C, ammonia is removed from the fiber material. The consequence is a good permanence of the flame retardant equipment.
Es ist häufig von Vorteil, wenn man die Komponente A und/oder die Komponente B nicht in reiner Form auf das Fasermaterial aufbringt, sondern in Form eines Gemischs mit Wasser, wenn man also sowohl Komponente A als auch Komponente B jeweils in Form eines Gemischs aufbringt, das Komponente A bzw. Komponente B und zusätzlich Wasser enthält. So kann man Komponente A beispielsweise in Form eines Gemischs einsetzen, das 50 bis 500 Gew.teile Wasser pro 100 Gew.teile Komponente A enthält, und Komponente B in Form eines Gemischs, das 20 bis 300 Gew.teile Wasser pro 100 Gew.teile Komponente B enthält. Eines oder beide dieser Gemische können weitere Komponenten enthalten, z.B. Polymaleinsäure oder teilhydrolysiertes Polymaleinsäureanhydrid. Der Zusatz von teil- oder vollhydrolysiertem Polymaleinsäureanhydrid liegt, wenn ein solcher Zusatz verwendet wird, bevorzugt im Bereich von 1 bis 5 Gew%, bezogen auf Gesamtgemisch, das Komponente A bzw. Komponente B und Wasser enthält.It is often advantageous if component A and / or component B are not applied in a pure form to the fiber material, but in the form of a mixture with water, that is, if both component A and component B are applied in the form of a mixture which contains component A or component B and additionally water. For example, component A can be used in the form of a mixture containing 50 to 500 parts by weight of water per 100 parts by weight of component A, and component B in the form of a mixture containing 20 to 300 parts by weight of water per 100 parts by weight Component B contains. One or both of these mixtures may contain other components, for example polymaleic acid or partially hydrolyzed polymaleic anhydride. The addition of partially or fully hydrolyzed polymaleic anhydride is, if such an additive is used, preferably in the range of 1 to 5% by weight, based on total mixture containing component A or component B and water.
Wenn Polymaleinsäure oder teilhydrolysiertes Polymaleinsäureanhydrid verwendet werden, setzt man dieses vorzugsweise einem Gemisch zu, das Komponente A und Wasser enthält. Dieser Zusatz bewirkt in einer Reihe von Fällen eine Erhöhung der Permanenz des flammhemmenden Effekts. Unter "Permanenz" ist in diesem Zusammenhang zu verstehen, dass die flammhemmenden Eigenschaften der Fasermaterialien im Großen und Ganzen erhalten bleiben, auch wenn das Fasermaterial in Kontakt mit Wasser kommt. Diese Erhöhung der Permanenz könnte daran liegen, dass die zusätzliche Verwendung von teilweise oder vollständig hydrolysiertem Polymaleinsäureanhydrid zu einer besseren Fixierung der Komponte A und/oder Komponente B auf dem Fasermaterial führt.When polymaleic acid or partially hydrolyzed polymaleic anhydride is used, it is preferably added to a mixture containing component A and water. This addition causes, in a number of cases, an increase in the permanence of the flame retardant effect. By "permanence" is meant in this context that the flame retardant properties of the fiber materials are generally retained, even when the fiber material comes in contact with water. This increase in permanence could be due to the fact that the additional use of partially or completely hydrolyzed polymaleic anhydride leads to a better fixation of the component A and / or component B on the fiber material.
Ferner kann es in manchen Fällen von Vorteil sein, zusätzlich einen Teilester der Orthophosphorsäure auf das Fasermaterial aufzubringen. Das Aufbringen dieses Teilesters kann gleichzeitig mit dem Aufbringen der Komponente A oder der Komponente B oder, was bevorzugt ist, getrennt davon in einem separaten Arbeitsgang erfolgen. Die Menge an Orthophosphorsäureteilester, die aufgebracht wird, liegt bevorzugt im Bereich von 2 bis 10 Gew%, bezogen auf wasserfreies Fasermaterial. Als Phosphorsäureteilester sind unter anderem Mono-oder Diester der Orthophosphorsäure mit 6 bis 12 Kohlenstoffatomen in der Alkoholkomponente des Esters geeignet, oder Gemische solcher Mono- und Diester. Ein Beispiel hierfür ist Diisooctyl-phosphat oder Diphenylphosphat oder Bis-(t-butyl-phenyl-) phosphat. Durch den Zusatz solcher Ester lässt sich vielfach die flammhemmende Wirkung steigern.Furthermore, in some cases it may be advantageous to additionally apply a partial ester of orthophosphoric acid to the fiber material. The application of this partial ester can be carried out simultaneously with the application of component A or component B or, what is preferred, separately therefrom in a separate operation. The amount of orthophosphoric acid partial ester which is applied is preferably in the range of 2 to 10% by weight, based on anhydrous fiber material. Suitable phosphoric acid partial esters include monoesters or diesters of orthophosphoric acid having 6 to 12 carbon atoms in the alcohol component of the ester, or mixtures of such mono- and diesters. An example of this is diisooctyl phosphate or diphenyl phosphate or bis (t-butyl-phenyl) phosphate. The addition of such esters can often increase the flame retardant effect.
Vorzugsweise enthalten weder Komponente A noch Komponente B noch die Gemische aus Komponente A oder Komponente B und Wasser Metalle oder Metallverbindungen, abgesehen von unwesentlichen Verunreinigungen. Dies ist ein Vorteil aus Kosten- und aus Umweltgründen, z.B. im Vergleich zum bekannten ZIRPRO® -Verfahren, wo mit Zirkoniumverbindungen gearbeitet wird, und außerdem wird dadurch vermieden, dass die fertigen Fasermaterialien durch Metallionen gefärbt sind. Gegebenenfalls können zwar in Komponente B in bis zu 50 % der an Phosphor gebundenen Hydroxygruppen die Wasserstoffatome durch Alkalimetall- oder Ammoniumionen ersetzt sein, jedoch ist dies nicht bevorzugt.Preferably neither component A nor component B nor the mixtures of component A or component B and water contain metals or metal compounds, apart from immaterial impurities. This is an advantage for cost and environmental reasons, e.g. compared to the well-known ZIRPRO® process, where zirconium compounds are used, and also prevents the finished fiber materials from being colored by metal ions. Optionally, although in component B up to 50% of the phosphorus-bonded hydroxy groups may be replaced by alkali metal or ammonium ions, hydrogen atoms are not preferred.
Das Aufbringen von Komponente A, Komponente B oder von einem Gemisch, das außer Komponente A oder Komponente B noch Wasser enthält, auf das Fasermaterial kann nach beliebigen Methoden erfolgen. Am günstigsten ist es, auf das Fasermaterial ein Gemisch zu applizieren, das Wasser und Komponente A enthält und anschließend ein Gemisch, das Wasser und Komponente B enthält. Die Applikation kann, wenn das Fasermaterial als textiles Flächengebilde vorliegt, mittels der bekannten Methode der Foulardierung erfolgen. Liegt das Fasermaterial in Form eines Garns vor, so kann die Applikation der Komponenten A und B erfolgen, indem man das Garn durch ein oder mehrere Bäder führt, die Komponente A bzw. Komponente B und Wasser enthalten, und anschließend die Garne trocknet. Es ist aber auch möglich, eine Spule, auf die das Garn aufgewickelt ist, im Rahmen eines Färbeprozesses in ein oder mehrere Bäder zu tauchen, welche Komponente A und/oder Komponente B enthalten, und anschließend die Spule zu trocknen.The application of component A, component B or of a mixture which contains water other than component A or component B, on the fiber material can be carried out by any desired methods. It is best to apply to the fiber material a mixture containing water and component A and then a mixture containing water and component B. The application can, if the fibrous material is present as a textile fabric, take place by means of the known method of padding. If the fiber material is in the form of a yarn, the application of components A and B can be carried out by passing the yarn through one or more baths containing component A or component B and water, and then drying the yarns. But it is also possible to use a coil on which the yarn is wound, dipping in a dyeing process in one or more baths containing component A and / or component B, and then to dry the coil.
Unabhängig davon, ob die Komponenten A und B jeweils als Gemisch mit Wasser oder in reiner Form auf das Fasermaterial aufgebracht werden, besteht eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens darin, dass das Gewichtsverhältnis der auf das Fasermaterial aufgebrachten Menge an Komponente A zur Menge an aufgebrachter Komponente B im Bereich von 1 : 1,8 bis 1 : 5,0 liegt, jeweils bezogen auf wasserfreie Produkte. Vorzugsweise liegt das Verhältnis im Bereich von 1 : 2,3 bis 1 : 3,5.Regardless of whether the components A and B are each applied as a mixture with water or in a pure form on the fiber material, a preferred embodiment of the method according to the invention is that the weight ratio of the applied to the fiber material amount of component A to the amount of applied component B ranges from 1: 1.8 to 1: 5.0, each based on anhydrous products. Preferably, the ratio is in the range of 1: 2.3 to 1: 3.5.
Die Menge an Komponente A und an Komponente B, die auf das Fasermaterial aufgebracht werden, wird vorzugsweise so bemessen, dass auf dem fertigen Fasermaterial 3 bis 10 Gew% Komponente A und 7 bis 20 Gew% Komponente B vorliegen, bezogen auf wasserfreies Fasermaterial.The amount of component A and component B, which are applied to the fiber material, is preferably such that on the finished fiber material 3 to 10% by weight of component A and 7 to 20% by weight of component B, based on anhydrous fiber material.
Die Komponente A ist ein Polyethylenimin. Wie bei Polymeren üblich, handelt es sich hierbei im Normalfall nicht um ein Produkt, das aus lauter gleichen Molekülen besteht, sondern das ein Gemisch aus Produkten unterschiedlicher Kettenlänge ist. Bei Polyethyleniminen kommt noch die aus der Literatur bekannte Tatsache hinzu, dass im Normalfall ein Gemisch verzweigter Polymerer vorliegt, dessen einzelne Moleküle sich auch noch in der Anzahl der Verzweigungseinheiten unterscheiden. Dies wird durch das unten näher erläuterte Verhältnis der Anzahl von sekundären zu primären Aminogruppen und zu tertiären Aminogruppen ausgedrückt. Polyethylenimine sind aus der Literatur bekannte Produkte. Sie können unter anderem durch Umsetzung von 1.2-Ethylendiamin mit 1.2-Dichlorethan hergestellt werden. Zur Durchführung des erfindungsgemäßen Verfahrens verwendet man bevorzugt Polyethylenimine, die durch Polymerisation von unsubstituiertem Aziridin (Ethylenimin) hergestellt werden können. Diese Polymerisation kann nach bekannten Methoden, gegebenenfalls unter Zusatz saurer Katalysatoren, z.B. Salzsäure, und gegebenenfalls in Gegenwart von Wasser durchgeführt werden.
Für das erfindungsgemäße Verfahren geeignete Polyethylenimine sind auf dem Markt erhältlich, z.B. von der Firma BASF, Deutschland (LUPASOL® -Typen und POLYMIN® -Typen). Component A is a polyethyleneimine. As is customary with polymers, this is normally not a product which consists of all the same molecules, but is a mixture of products of different chain lengths. In the case of polyethyleneimines, the fact known from the literature is added that under normal conditions there is a mixture of branched polymers whose individual molecules also differ in the number of branching units. This is expressed by the ratio of the number of secondary to primary amino groups as detailed below and to tertiary amino groups. Polyethyleneimines are products known from the literature. They can be prepared inter alia by reacting 1,2-ethylenediamine with 1,2-dichloroethane. To carry out the process according to the invention, preference is given to using polyethyleneimines which can be prepared by polymerization of unsubstituted aziridine (ethyleneimine). This polymerization can be carried out by known methods, if appropriate with addition of acidic catalysts, for example hydrochloric acid, and optionally in the presence of water.
Polyethyleneimines suitable for the process according to the invention are available on the market, for example from BASF, Germany (LUPASOL® grades and POLYMIN® grades).
Die
Polyethylenimine, ihre Herstellung und Eigenschaften werden auch in
Polyethyleneimines, their preparation and properties are also used in
Die für das erfindungsgemäße Verfahren als Komponente A geeigneten Polyethylenimine sind verzweigt. Das heißt, dass das Polymer, welches Endgruppen der Formel
H2N―CH2―CH2―
und innerhalb der Polymerkette Einheiten der Formel
-CH2-CH2-NH-CH2-CH2-NH-
aufweist, zusätzlich innerhalb der Kette noch Einheiten der Formel
Das Polymer enthält also primäre, sekundäre und tertiäre Aminogruppen.
Damit die Durchführung des erfindungsgemäßen Verfahrens gute Effekte bezüglich flammhemmender Eigenschaften der Fasermaterialien liefert, müssen die zahlenmäßigen Verhältnisse zwischen den einzelnen Aminogruppen Werte in einem bestimmten Bereich annehmen. So muß in Komponente A das Verhältnis der Anzahl sekundärer Aminogruppen zur Anzahl primärer Aminogruppen im Bereich von 1,00 : 1 bis 2,50 : 1 liegen, und das Verhältnis der Anzahl sekundärer Aminogruppen zur Anzahl tertiärer Aminogruppen im Bereich von 1,20 : 1 bis 2,00 : 1. Diese zahlenmäßigen Werte lassen sich steuern über die Parameter bei der Herstellung der Polyethylenimine.
Die in einem bestimmten Polyethylenimin oder Gemisch von Polyethyleniminen vorliegenden Werte für die genannten zahlenmäßigen Verhältnisse der verschiedenen Aminogruppen lassen sich über 13C-NMR-Spektroskopie bestimmen. Dies wird erläutert in "
H 2 N-CH 2 -CH 2 -
and within the polymer chain, units of the formula
-CH 2 -CH 2 -NH-CH 2 -CH 2 -NH-
additionally has units of the formula within the chain
The polymer thus contains primary, secondary and tertiary amino groups.
In order for the performance of the method according to the invention to provide good effects with respect to flame retardant properties of the fiber materials, the numerical ratios between the individual amino groups must assume values in a certain range. Thus, in component A, the ratio of the number of secondary amino groups to the number of primary amino groups must be in the range of 1.00: 1 to 2.50: 1, and the ratio of the number of secondary amino groups to the number of tertiary amino groups in the range of 1.20: 1 to 2.00: 1. These numerical values can be controlled via the parameters in the production of polyethyleneimines.
The values for the numerical ratios of the various amino groups present in a particular polyethyleneimine or mixture of polyethylenimines can be determined by 13 C-NMR spectroscopy. This is explained in "
Komponente A, die, wie bei Polymeren üblich, normalerweise ein Gemisch von Polymeren ist und aus Polyethyleniminmolekülen unterschiedlichen Molgewichts und unterschiedlichen Verzweigungsgrades besteht, besitzt ein Gewichtsmittel des Molgewichts im Bereich von 5.000 bis 1.500.000, vorzugsweise im Bereich von 10.000 bis 1.000.000. Der im Einzelfall vorliegende Wert für dieses mittlere Molgewicht lässt sich nach Verfahren bestimmen, wie sie aus der Polymerliteratur bekannt sind, z.B. mittels Gelpermeationschromatographie und Detektion mittels Lichtstreuung. Hierzu kann man folgendermaßen vorgehen:
- Man verwendet als Säule eine oder mehrere "PSS-Suprema"-Typen (beziehbar von "Polymer Standards Service GmbH", Mainz, DE), die auf den vorgesehenen Molgewichtsbereich eingestellt sind; Elutionsmittel 1,5%ige Ameisensäure in Wasser; Mehrwinkel-Lichtstreudetektor
- MALLS (ebenfalls beziehbar u.a. von "Polymer Standards Service"); ein interner Standard kann gegebenenfalls zusätzlich verwendet werden.
Das mittlere Molgewicht von Polyethyleniminen lässt sich steuern durch Variation der Parameter bei ihrer Herstellung.Component A, which, as is usual in polymers, is normally a mixture of polymers and consists of polyethyleneimine molecules of different molecular weight and different degrees of branching, has a weight average molecular weight in the range of 5,000 to 1,500,000, preferably in the range of 10,000 to 1,000,000. The individual value for this average molecular weight can be determined by methods known from the polymer literature, for example by gel permeation chromatography and detection by means of Light scattering. This can be done as follows:
- The column used is one or more "PSS Suprema" types (available from "Polymer Standards Service GmbH", Mainz, DE), which are adjusted to the intended molecular weight range; Eluant 1.5% formic acid in water; Multi-angle light scattering detector
- MALLS (also available from, among others, "Polymer Standards Service"); an internal standard may be used in addition.
The average molecular weight of polyethyleneimines can be controlled by varying the parameters in their preparation.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, dass Komponente A ein
Polyethylenimin ist, das durch Polymerisation von Ethylenimin gebildet wird und das folgende Struktur aufweist (Formel (V))
wobei die einzelnen Einheiten, welche tertiäre Aminogruppen enthalten und die einzelnen Einheiten, welche sekundäre Aminogruppen enthalten, beliebig über die Polymerkette verteilt sein können,
wobei
b größer als a ist und wobei a und b solche Werte besitzen, dass die in Anspruch 1 genannten Bedingungen für das Molgewicht und für die zahlenmäßigen Verhältnisse der Aminogruppen untereinander erfüllt sind
oder wobei Komponente A ein Gemisch solcher Polyethylenimine ist.
Wie erwähnt, ist Komponente A normalerweise ein Gemisch von Polyethyleninimen. Die oben genannte bevorzugte Ausführungsform besteht also im Normalfall darin, dass Komponente A ein Gemisch von Verbindungen der Formel (V) ist. Die Werte von a und b in den Verbindungen der Formel (V) müssen natürlich so gewählt werden, dass die an dem Gemisch ermittelten Werte für die zahlenmäßigen Verhältnisse der einzelnen Aminogruppen zueinander und für das mittlere Molgewicht in den oben und in Anspruch 1 genannten Bereichen liegen. Die Steuerung dieser Werte kann, wie erwähnt, über die Parameter bei der Herstellung der Polyethylenimine erfolgen.A preferred embodiment of the method according to the invention is that component A a
Polyethyleneimine formed by polymerization of ethyleneimine and having the following structure (formula (V))
wherein the individual units which contain tertiary amino groups and the individual units which contain secondary amino groups can be distributed as desired over the polymer chain,
in which
b is greater than a and wherein a and b have such values that the conditions mentioned in claim 1 for the molecular weight and for the numerical ratios of the amino groups with one another are met
or wherein component A is a mixture of such polyethyleneimines.
As mentioned, component A is normally a mixture of polyethylenimines. The abovementioned preferred embodiment thus normally consists in component A being a mixture of compounds of the formula (V). The values of a and b in the compounds of the formula (V) must, of course, be chosen so that the values for the ratios of the individual amino groups to one another and for the average molecular weight determined in the mixture are in the ranges stated above and in claim 1 , The control of these values can, as mentioned, be done via the parameters in the production of the polyethyleneimines.
Komponente B kann auch ein Gemisch von Verbindungen sein, die aus Verbindungen der Formel (I), der Formel (II) und der Formel (III) ausgewählt sind.
In Formel (I) bedeutet R einen linearen oder verzweigten Alkylrest. Dieser Alkylrest enthält für den Fall, dass der unten genannte Rest R1 eine Hydroxygruppe ist, 1 bis 7 Kohlenstoffatome. Falls R1 Wasserstoff ist, enthält der Rest R 3 bis 7 Kohlenstoffatome.
Der Rest R1 in Formel (1) steht für H oder OH.
In Formel (I) steht der Rest R2 für den Rest
In formula (I), R represents a linear or branched alkyl radical. This alkyl group contains 1 to 7 carbon atoms in the case that the below-mentioned R 1 is a hydroxy group. If R 1 is hydrogen, the radical R contains 3 to 7 carbon atoms.
The radical R 1 in formula (1) is H or OH.
In formula (I), the radical R 2 is the radical
Der Rest R3 in Formel (1) kann für Wasserstoff stehen. Bevorzugt jedoch steht er für einen Rest R2. Hierdurch lässt es sich erreichen, dass der Gehalt an Phosphor auf dem fertigen Faserprodukt höher ist als für den Fall R3=H, wodurch im Normalfall ein verbesserter Flammschutz resultiert.
In Formel (II) kann y die Werte 0, 1 oder 2 annehmen. Vorzugsweise besitzt y den Wert 0, was analog zu dem oben geschilderten Fall in einer Erhöhung des Phosphorgehalts auf dem Faserprodukt resultiert.
Alle in Verbindungen der Formel (III) anwesenden Reste R4 stehen unabhängig voneinander für Wasserstoff oder für
In formula (II) y can take the values 0, 1 or 2. Preferably, y has the value 0, which analogously to the case described above results in an increase in the phosphorus content on the fiber product.
All radicals R 4 present in compounds of the formula (III) independently of one another represent hydrogen or
Nicht alle in Komponente B vorliegenden Phosphonsäuren müssen in vollständig nicht-neutralisierter Form vorliegen. Vielmehr können in bis zu 50 % der vorliegenden, an Phosphor gebundenen, OH-Gruppen die sauren Wasserstoffatome durch Alkalimetall oder Ammoniumionen ersetzt sein. Vorzugsweise jedoch liegen alle Phosphonsäuren von Komponente B in vollständig nicht-neutralisierter Form vor, sodaß also alle OH-Gruppen in saurer Form vorliegen. Phosphonsäuren der Formeln (I), (II) und (III) sind marktübliche Produkte, z.B. Masquol P 210-1 der Firma Protex-Extrosa oder Briquest 301-50 A der Firma Rhodia oder die Produkte Cublen D50 (Fa. Zschimmer & Schwarz, DE), oder Diquest 2060 S (Fa. Solutia, Belgien). Phosphonsäuren der Formeln (I), (II) und (III) lassen sich nach aus der Literatur allgemein bekannten Methoden herstellen.Not all phosphonic acids present in component B must be in completely unneutralized form. Rather, in up to 50% of the present, bonded to phosphorus, OH groups, the acidic hydrogen atoms may be replaced by alkali metal or ammonium ions. Preferably, however, all the phosphonic acids of component B are present in completely unneutralized form, so that therefore all OH groups are present in acidic form. Phosphonic acids of formulas (I), (II) and (III) are commercially available products, e.g. Masquol P 210-1 from Protex-Extrosa or Briquest 301-50 A from Rhodia or the products Cublen D50 (from Zschimmer & Schwarz, DE), or Diquest 2060 S (from Solutia, Belgium). Phosphonic acids of the formulas (I), (II) and (III) can be prepared by methods generally known from the literature.
Eine besonders vorteilhafte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, dass Komponente B ein Gemisch aus Phosphonsäuren der Formel (II) und der Formel (III) ist, die beide in vollständig nicht-neutralisierter Form vorliegen.
In einem solchen Gemisch kann das Mischungsverhältnis von Phosphonsäure der Formel (II) und Phosphonsäure der Formel (III) beliebige Werte annehmen. So kann das Gewichtsverhältnis der beiden Typen von Phosphonsäure Werte von 0 : 100 bis 100 : 0 annehmen. Gute Ergebnisse werden beispielsweise erzielt, wenn man als Komponente B ein Gemisch verwendet, das 70 bis 95 Gew% an einer Verbindung oder einem Gemisch von Verbindungen der Formel (II) und 5 bis 30 Gew% an einer Verbindung oder einem Gemisch von Verbindungen der Formel (III) enthält. Besonders günstig ist es, hierbei eine Verbindung der Formel (II) zu verwenden, bei der
y = 0 ist.A particularly advantageous embodiment of the process according to the invention is characterized in that component B is a mixture of phosphonic acids of the formula (II) and of the formula (III), both of which are in completely unneutralized form.
In such a mixture, the mixing ratio of phosphonic acid of the formula (II) and phosphonic acid of the formula (III) may assume any values. Thus, the weight ratio of the two types of phosphonic acid can assume values of 0: 100 to 100: 0. Good results are achieved, for example, when using a mixture as component B, which contains 70 to 95% by weight of a compound or a mixture of compounds of the formula (II) and 5 to 30% by weight of a compound or a mixture of compounds of the formula (III). It is particularly advantageous to use a compound of the formula (II) in which
y = 0.
Als Komponente B können auch eine Verbindung der Formel (I) oder ein Gemisch von Verbindungen der Formel (I) oder eine Verbindung der Formel (II) oder ein Gemisch von Verbindungen der Formel (II) oder eine Verbindung der Formel (III) oder ein Gemisch von Verbindungen der Formel (III) verwendet werden. Besonders gute Ergebnisse lassen sich erhalten, wenn Komponente B zu 100 % aus einer Verbindung der Formel (II) oder einem Gemisch von Verbindungen der Formel (II) besteht, wobei in diesen Fällen y in Formel (II) den Wert 0 oder 1 besitzt.As component B, a compound of formula (I) or a mixture of compounds of formula (I) or a compound of formula (II) or a mixture of compounds of formula (II) or a compound of formula (III) or Mixture of compounds of formula (III) can be used. Particularly good results can be obtained if component B consists to 100% of a compound of formula (II) or a mixture of compounds of formula (II), in which case y in formula (II) has the value 0 or 1.
Die Fasermaterialien, welche nach dem erfindungsgemäßen Verfahren behandelt werden, liegen in Form eines textilen Flächengebildes oder in Form eines Garns, vor. Das Garn kann aus Endlosfäden bestehen oder aus Spinnfasern durch Ringspinnen oder Open-End-Spinnen hergestellt worden sein. Als textile Flächengebilde kommen Gewebe, Maschenware oder Vliese (nonwovens) in Betracht. Vorzugsweise werden Gewebe für die Durchführung des erfindungsgemäßen Verfahrens verwendet. Die Fasermaterialien enthalten, wie oben erwähnt, vorzugsweise 30 bis 100 Gew% Wolle. Gewebe, die zu 100 % aus Wolle bestehen, sind besonders gut für das erfindungsgemäße Verfahren geeignet. Die Herkunft der Wolle ist hierbei nicht entscheidend, die Qualität der Wolle beeinflusst aber natürlich die Eigenschaften des Endartikels. Die nach dem erfindungsgemäßen Verfahren behandelten Fasermaterialien lassen sich zur Herstellung von Gebrauchstextilien verwenden, wie z.B. Autositze, Gardinen, Teppiche, usw.The fiber materials which are treated by the process according to the invention are in the form of a textile fabric or in the form of a yarn. The yarn may consist of continuous filaments or may have been made of staple fibers by ring spinning or open-end spinning. Textile fabrics are wovens, knits or fleeces (nonwovens). Preferably, tissues are used for carrying out the method according to the invention. As mentioned above, the fiber materials preferably contain from 30 to 100% by weight of wool. Fabrics consisting of 100% wool are particularly well suited to the process of the invention. The origin of the wool is not decisive, but the quality of the wool naturally influences the properties of the final article. The fiber materials treated by the process of the invention can be used to make consumer textiles, such as e.g. Car seats, curtains, carpets, etc.
Die Erfindung wird nunmehr durch Ausführungsbeispiele näher veranschaulicht.The invention will now be illustrated by exemplary embodiments.
4,8 kg einer kommerziell erhältlichen wässrigen Lösung (LUPASOL® P, BASF, DE), die 50 Gew% Wasser und 50 Gew% Polyethylenimin enthielt, wurden mit 4,8 kg Wasser und 0,35 kg einer 50 %igen wässrigen Lösung eines hydrolysierten Polymaleinsäureanhydrids gemischt. Das fertige Gemisch (nachfolgend "Gemisch 1a" genannt) enthielt also etwa 24 Gew% Komponente A.4.8 kg of a commercially available aqueous solution (LUPASOL® P, BASF, DE) containing 50% by weight of water and 50% by weight of polyethylenimine were mixed with 4.8 kg of water and 0.35 kg of a 50% aqueous solution of hydrolyzed polymaleic anhydride. The finished mixture (hereinafter referred to as "mixture 1a") thus contained about 24% by weight of component A.
9,2 kg einer wässrigen Lösung, die 40 Gew% Wasser und 60 Gew% einer Phosphonsäure der oben angegebenen Formel (I) (mit
Dieses Beispiel betrifft die Behandlung von Fasermaterialien, welche in Form von Garnen vorliegen, mit Komponenten A und B.This example relates to the treatment of fiber materials which are in the form of yarns with components A and B.
In 3 getrennt durchgeführten Versuchen wurden 3 verschiedene Arten (2a, 2b, 2c) von Spinnfasergarnen jeweils auf Kreuzspulen gewickelt und jeweils in eine herkömmliche Färbeapparatur installiert. Garn 2a war ein blaues, sauer angefärbtes Spinnfasergarn aus 100 % Wolle, Garn 2b ein braunes Spinnfasergarn aus 90 Gew% Wolle und 10 Gew% Polyamid, Garn 2c ein blaugraues Spinnfasergarn aus 90 Gew% Wolle und 10 Gew% Polyamid.
Die Färbeapparatur wurde in allen 3 Versuchen zuerst mit jeweils der 10-fachen Menge Wasser von Raumtemperatur, bezogen auf das Gewicht des betreffenden Garns (ohne Kreuzspule berechnet), beschickt.
Anschließend wurde das Wasser aus der Apparatur entfernt, und es wurde bei Raumtemperatur Gemisch 1 c zugegeben. Gemisch 1c enthielt 50 Gew% Gemisch 1 a (gemäß Beispiel 1 a) und 50 Gew% Wasser. Gemisch 1 c enthielt also Komponente A. Die Menge an zugegebenem Gemisch 1c betrug in allen 3 Versuchen 12 Gew%, bezogen auf das Gewicht des betreffenden Garns, d.h. bezogen auf das Gewicht von Garn 2a bzw. 2b bzw. 2c. In allen 3 Versuchen wurden die Kreuzspulen in der Färbeapparatur bei Raumtemperatur 10 Minuten lang der Einwirkung von Gemisch 1 c ausgesetzt. Anschließend wurde die Apparatur 5 Minuten lang mit Wasser gespült und das Spülwasser entfernt.
Nunmehr wurde in die Apparatur bei Raumtemperatur Gemisch 1 d gegeben. Gemisch 1 d enthielt 50 Gew% des gemäß Beispiel 1b) hergestellten Gemischs 1 b und 50 Gew% Wasser. Somit enthielt Gemisch 1 d Komponente B). Die Menge an Gemisch 1 d, welche in jedem der 3 Versuche in die Apparatur gegeben wurde, betrug 12 Gew%, bezogen auf das Gewicht von Garn 2a bzw. 2b bzw. 2c. Die Kreuzspulen wurden 10 Minuten lang bei Raumtemperatur der Einwirkung von Gemisch 1d ausgesetzt. Anschließend wurde die Apparatur zweimal jeweils mit Wasser von Raumtemperatur gespült. Die Kreuzspulen wurden in allen Versuchen daraufhin aus der Apparatur entnommen und 15 Minuten bei 120°C getrocknet. Anschließend wurde aus den jeweiligen Garnen je 1 Probe Maschenware hergestellt.In 3 separate experiments 3 different types (2a, 2b, 2c) of spun yarns were each wound on cheeses and each installed in a conventional dyeing machine. Yarn 2a was a blue, spun yarn of 100% wool dyed yarn, yarn 2b a brown spun yarn of 90% by weight of wool and 10% by weight of polyamide, yarn 2c by a blue-gray spun yarn of 90% by weight of wool and 10% by weight of polyamide.
The dyeing apparatus was charged in all three experiments first with 10 times the amount of water at room temperature, based on the weight of the yarn in question (calculated without cross-wound bobbin).
The water was then removed from the apparatus and 1C was added at room temperature. Mixture 1c contained 50% by weight of mixture 1 a (according to Example 1 a) and 50% by weight of water. Mixture 1c thus contained component A. The amount of mixture 1c added was 12% by weight, based on the weight of the respective yarn, ie based on the weight of yarn 2a or 2b or 2c in all 3 tests. In all 3 experiments, the cheeses were exposed in the dyeing apparatus at room temperature for 10 minutes to the action of mixture 1 c. Subsequently, the apparatus was rinsed with water for 5 minutes and the rinse water was removed.
The mixture was then added to the apparatus at room temperature for 1 d. Mixture 1 d contained 50% by weight of the mixture 1 b prepared according to Example 1b) and 50% by weight of water. Thus, mixture contained 1 d component B). The amount of mixture 1 d, which was added to the apparatus in each of the 3 experiments, was 12% by weight, based on the weight of yarn 2a, 2b and 2c, respectively. The cheeses were exposed to the action of mixture 1d for 10 minutes at room temperature. Subsequently, the apparatus was rinsed twice each with room temperature water. The cheeses were thereupon in all attempts removed from the apparatus and dried at 120 ° C for 15 minutes. Subsequently, 1 sample of knit fabric was made from the respective yarns.
Alle 3 Versuche von Beispiel 2 wurden wiederholt mit dem einzigen Unterschied, dass die Menge an Gemisch 1 c und an Gemisch 1 d, welche man in die Färbeapparatur gab, nicht 12 Gew%, bezogen auf Garngewicht, betrug, sondern nur 6 Gew%.All 3 experiments of Example 2 were repeated with the only difference that the amount of mixture 1 c and mixture 1 d, which was added to the dyeing machine, not 12 wt%, based on yarn weight, but only 6 wt%.
An den 6 Proben Maschenware aus den Beispielen 2 und 3 wurden Bestimmungen der flammhemmenden Eigenschaften durchgeführt. Bei den Proben aus Garn 2a und Garn 2c wurde die Bestimmung nach DIN 4102 B2 durchgeführt, bei Garn 2b nach Methode "Federal Motor Vehicle Safety Standard (FMVSS) 302". Diese Methode ist beschrieben in "
Dieses Beispiel betrifft die Behandlung von Geweben nach dem erfindungsgemäßen Verfahren. Als Gewebe diente Material aus 100 % Wolle, rot gefärbt, 205 g/m2.
Das Material wurde über Foulardierung mit einer Flotte behandelt, welche folgendermaßen hergestellt wurde:This example relates to the treatment of tissues by the method of the invention. The fabric used was 100% wool, dyed red, 205 g / m 2 .
The material was treated via padding with a liquor prepared as follows:
35 g einer 25 %igen wässrigen Lösung eines Polyethylenimins (Komponente A) wurden mit 45 g einer 50 %igen wässrigen Lösung einer Phosphonsäure der Formel (II) mit y = 0 (Komponente B) gemischt. Zu der Mischung gab man 21 g einer 22 %igen wässrigen Ammoniaklösung. Unter Rühren entstand eine klare Lösung vom pH 7,5. Diese Lösung wurde im Gewichtsverhältnis 1:1 1 mit Wasser verdünnt. Die erhaltene Mischung wurde als Foulardierungsflotte verwendet.
Nach der Foulardierung wurde bei 150°C/10 Minuten getrocknet. Danach enthielt das Fasermaterial 9 % Feststoffauflage, d.h. das Gewicht des Fasermaterials war um 9 % höher als das Gewicht des Fasermaterials vor Foulardierung.35 g of a 25% aqueous solution of a polyethyleneimine (component A) were mixed with 45 g of a 50% aqueous solution of a phosphonic acid of the formula (II) with y = 0 (component B). To the mixture was added 21 g of a 22% aqueous ammonia solution. With stirring, a clear solution of pH 7.5 was formed. This solution was diluted in the weight ratio 1: 1 1 with water. The resulting mixture was used as a padding liquor.
After padding was dried at 150 ° C / 10 minutes. Thereafter, the fiber material contained 9% solids coverage, ie the weight of the fiber material was 9% higher than the weight of the fiber material prior to padding.
Beispiel 4 wurde wiederholt, mit dem Unterschied, dass nicht 45 g der wässrigen Phosphonsäurelösung verwendet wurden, sondern nur 30 g, und dass nicht bei 150°C getrocknet wurde, sondern bei 110°C. Die Feststoffauflage betrug 8,6 %.Example 4 was repeated, with the difference that not 45 g of the aqueous phosphonic acid solution were used, but only 30 g, and that was not dried at 150 ° C, but at 110 ° C. The solids coverage was 8.6%.
Beispiel 4 wurde wiederholt mit dem einzigen Unterschied, dass nicht ein Gewebe aus 100 % Wolle verwendet wurde, sondern ein Gewebe aus 90 Gew% Wolle und 10 Gew% Polyamid.Example 4 was repeated with the only difference that not a fabric of 100% wool was used, but a fabric of 90 wt% wool and 10 wt% polyamide.
An den gemäß Beispielen 4, 5 und 6 behandelten Geweben wurden die flammhemmenden Eigenschaften bestimmt und zwar über die Brennzeiten. Die Brennzeit (BZ) bezeichnet die Zeit in Sekunden, während der das betreffende Muster noch nachbrennt, nachdem es 3 Sekunden einer Flamme ausgesetzt war und diese Flamme dann entfernt wurde. Ein höherer Wert für BZ bedeutet also schlechtere flammhemmende Eigenschaften. Die Bestimmung der Brennzeit erfolgte nach DIN 54336 (Ausgabe November 1986). Die Brennzeiten wurden sowohl an den Gewebeproben bestimmt, die unmittelbar nach der erwähnten Trocknung erhalten wurden als auch an den Proben gleicher Provenienz, die jedoch nach dem Trocknen noch gewaschen worden waren (reines Wasser bei 40°C/20 Minuten).On the fabrics treated according to Examples 4, 5 and 6, the flame retardant properties were determined over the firing times. The burn time (BZ) is the time in seconds that the pattern in question still burns after being exposed to a flame for 3 seconds and then that flame is removed. A higher value for BZ thus means worse flame retardant properties. The burning time was determined according to DIN 54336 (November 1986 issue). The firing times were determined both on the tissue samples obtained immediately after the mentioned drying and on the samples of the same origin, which were still washed after drying (pure water at 40 ° C./20 minutes).
Die Ergebnisse zeigt Tabelle 1
Es ist zu sehen, dass im Fall von Beispiel 5 die Menge an Komponente B noch ausreichend war, um gute flammhemmende Eigenschaften am ungewaschenen Gewebe zu bewirken, dass aber, um gute Permanenz gegenüber Waschvorgängen zu erzielen, höhere Auflagen an Komponente B nötig sind.It can be seen that in the case of Example 5, the amount of component B was still sufficient to effect good flame retardant properties on the unwashed fabric, but to achieve good permanence over laundering, higher runs of component B are needed.
Claims (8)
oder wobei Komponente B ein Gemisch von Verbindungen ist, die aus Verbindungen der Formel (I), (II) oder (III) ausgewählt sind,
wobei
y die Werte 0, 1 oder 2 annehmen kann und vorzugsweise den Wert 0 besitzt,
R1 für H oder OH steht,
R für einen linearen oder verzweigten Alkylrest steht, der 1 bis 7 Kohlenstoffatome enthält, wenn R1 = OH ist und 3 bis 7 Kohlenstoffatome enthält, wenn R1 = H ist
wobei
R2 für
wobei R3 für H oder R2, vorzugsweise für R2 steht und wobei
alle Reste R4 unabhängig voneinander für H oder für
wobei t 0 oder eine Zahl von 1 bis 10 ist.Process for the flame retardant finishing of a fibrous material which is in the form of a textile fabric or in the form of a yarn and contains less than 20% by weight of cellulose fibers, wherein the fibrous material is treated successively or simultaneously with a component A and a component B, wherein component A is a branched one Polyethyleneimine containing primary, secondary and tertiary amino groups and having a weight average molecular weight in the range of 5,000 to 1,500,000, preferably 10,000 to 1,000,000, and in which the ratio of secondary amino groups to primary amino groups in the range of 1 , 00: 1 to 2.50: 1 and the numerical ratio of secondary amino groups to tertiary amino groups is in the range of 1.20: 1 to 2.00: 1, or wherein component A is a mixture of such polyethylenimimes, wherein component B is a Phosphonic acid of the formula (I), (II) or the formula (III)
or wherein component B is a mixture of compounds selected from compounds of formula (I), (II) or (III),
in which
y can assume the values 0, 1 or 2 and preferably has the value 0,
R 1 is H or OH,
R is a linear or branched alkyl radical containing 1 to 7 carbon atoms when R 1 = OH and containing 3 to 7 carbon atoms when R 1 = H
in which
R 2 for
wherein R 3 is H or R 2 , preferably R 2 and wherein
all radicals R 4 independently of one another for H or for
where t is 0 or a number from 1 to 10.
wobei die einzelnen Einheiten, welche tertiäre Aminogruppen enthalten und die einzelnen Einheiten, welche sekundäre Aminogruppen enthalten, beliebig über die Polymerkette verteilt sein können,
wobei
b größer als a ist und wobei a und b solche Werte besitzen, dass die in Anspruch 1 genannten Bedingungen für das Molgewicht und für die zahlenmäßigen Verhältnisse der Aminogruppen untereinander erfüllt sind
oder wobei Komponente A ein Gemisch solcher Polyethylenimine ist.A process according to claim 1 or 2, characterized in that component A is a polyethyleneimine formed by polymerization of ethyleneimine and having the following structure (formula (V))
wherein the individual units which contain tertiary amino groups and the individual units which contain secondary amino groups can be distributed as desired over the polymer chain,
in which
b is greater than a and wherein a and b have such values that the conditions mentioned in claim 1 for the molecular weight and for the numerical ratios of the amino groups with one another are met
or wherein component A is a mixture of such polyethyleneimines.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05006920A EP1707665A1 (en) | 2005-03-30 | 2005-03-30 | Process for flame-proofing of fibrous materials |
| CA002602238A CA2602238A1 (en) | 2005-03-30 | 2006-02-25 | Process for the flame-retardant treatment of fiber materials |
| PCT/EP2006/001750 WO2006102962A1 (en) | 2005-03-30 | 2006-02-25 | Process for the flame-retardant treatment of fiber materials |
| EP06707275A EP1877616A1 (en) | 2005-03-30 | 2006-02-25 | Process for the flame-retardant treatment of fiber materials |
| CNA2006800192537A CN101189383A (en) | 2005-03-30 | 2006-02-25 | Method for flame retardant treatment of fibrous materials |
| JP2008503386A JP2008534798A (en) | 2005-03-30 | 2006-02-25 | Flame retardant treatment method for textile materials |
| US11/910,106 US20090068369A1 (en) | 2005-03-30 | 2006-02-25 | Process for the flame-retardant treatment of fiber materials |
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| Application Number | Priority Date | Filing Date | Title |
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| EP05006920A EP1707665A1 (en) | 2005-03-30 | 2005-03-30 | Process for flame-proofing of fibrous materials |
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| EP05006920A Withdrawn EP1707665A1 (en) | 2005-03-30 | 2005-03-30 | Process for flame-proofing of fibrous materials |
| EP06707275A Withdrawn EP1877616A1 (en) | 2005-03-30 | 2006-02-25 | Process for the flame-retardant treatment of fiber materials |
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| EP (2) | EP1707665A1 (en) |
| JP (1) | JP2008534798A (en) |
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| WO2008152018A1 (en) * | 2007-06-13 | 2008-12-18 | Basf Se | Method for producing formed bodies |
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| EP1935935A1 (en) * | 2006-12-20 | 2008-06-25 | Huntsman Textile Effects (Germany) GmbH | Compound for treating fibre materials |
| EP2133461A1 (en) * | 2008-06-12 | 2009-12-16 | Huntsman Textile Effects (Germany) GmbH | Compound for treating fibrous material, in particular by the method of extraction |
| EP2402416A1 (en) * | 2010-06-30 | 2012-01-04 | Huntsman Textile Effects (Germany) GmbH | Flame retardant compound for cotton wool items |
| ITTO20130670A1 (en) * | 2013-08-05 | 2015-02-06 | Torcitura Padana S P A | CELLULOSIC SUBSTRATE WITH ANTI-FLAME PROPERTIES AND RELATED PRODUCTION PROCEDURE |
| CN103981707A (en) * | 2014-04-23 | 2014-08-13 | 桐乡市濮院毛针织技术服务中心 | Wool fabric flame retardation finishing method |
| US12320039B2 (en) * | 2016-04-22 | 2025-06-03 | General Recycled | Protective fabric and process of manufacturing same |
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| CN110512419B (en) * | 2019-08-08 | 2021-11-02 | 东华大学 | A kind of antibacterial flame retardant cellulose and its preparation and application |
| CN112717894A (en) * | 2020-12-17 | 2021-04-30 | 宜宾惠美纤维新材料股份有限公司 | Adsorption modifier for cellulose fiber, adsorptive cellulose fiber and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3874912A (en) * | 1969-09-30 | 1975-04-01 | Cotton Inc | Rendering fibrous material flame retardant |
| JPS5035499A (en) * | 1973-07-26 | 1975-04-04 | ||
| US4086385A (en) * | 1975-11-05 | 1978-04-25 | The United States Of America As Represented By The Secretary Of Agriculture | Flame retarded textiles via deposition of polymers from oligomeric vinylphosphonate and polyamino compounds |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2286726A (en) * | 1939-01-06 | 1942-06-16 | Du Pont | Process of flameproofing cellulosic material and products thereof |
| US3963437A (en) * | 1974-04-15 | 1976-06-15 | Cotton Incorporated | Flame retardant process for cellulosic material including cyanamide, phosphonic acid, antimony oxide and polymeric halogen-containing material |
| DE3003648A1 (en) * | 1980-02-01 | 1981-08-06 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PREPARATION OF WATER-SOLUBLE, NITROGEN-CONDENSING PRODUCTS AND THE USE THEREOF IN PAPER PRODUCTION |
| DE4137621A1 (en) * | 1991-11-15 | 1993-05-19 | Wolman Gmbh Dr | WOOD PRESERVATIVES |
| DE4244194A1 (en) * | 1992-12-24 | 1994-06-30 | Basf Ag | Water-soluble condensation products from compounds containing amino groups and crosslinking agents, processes for their preparation and their use |
| DE19545874A1 (en) * | 1995-12-08 | 1997-06-12 | Basf Ag | Process for the continuous production of homopolymers of ethyleneimine |
| US6451961B2 (en) * | 2000-02-03 | 2002-09-17 | Nippon Shokubai Co Ltd | Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor |
-
2005
- 2005-03-30 EP EP05006920A patent/EP1707665A1/en not_active Withdrawn
-
2006
- 2006-02-25 EP EP06707275A patent/EP1877616A1/en not_active Withdrawn
- 2006-02-25 CA CA002602238A patent/CA2602238A1/en not_active Abandoned
- 2006-02-25 US US11/910,106 patent/US20090068369A1/en not_active Abandoned
- 2006-02-25 WO PCT/EP2006/001750 patent/WO2006102962A1/en not_active Ceased
- 2006-02-25 CN CNA2006800192537A patent/CN101189383A/en active Pending
- 2006-02-25 JP JP2008503386A patent/JP2008534798A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3874912A (en) * | 1969-09-30 | 1975-04-01 | Cotton Inc | Rendering fibrous material flame retardant |
| JPS5035499A (en) * | 1973-07-26 | 1975-04-04 | ||
| US4086385A (en) * | 1975-11-05 | 1978-04-25 | The United States Of America As Represented By The Secretary Of Agriculture | Flame retarded textiles via deposition of polymers from oligomeric vinylphosphonate and polyamino compounds |
Non-Patent Citations (1)
| Title |
|---|
| DATABASE WPI Section Ch Week 197546, Derwent World Patents Index; Class A14, AN 1975-76291W, XP002355665 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008152018A1 (en) * | 2007-06-13 | 2008-12-18 | Basf Se | Method for producing formed bodies |
| US8512618B2 (en) | 2007-06-13 | 2013-08-20 | Basf Se | Process for the production of moldings |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090068369A1 (en) | 2009-03-12 |
| EP1877616A1 (en) | 2008-01-16 |
| WO2006102962A1 (en) | 2006-10-05 |
| CA2602238A1 (en) | 2006-10-05 |
| CN101189383A (en) | 2008-05-28 |
| JP2008534798A (en) | 2008-08-28 |
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