EP0120316A2 - Fibres, fils, matériaux textiles, feuilles et produits similaires ayant des propriétés améliorées - Google Patents

Fibres, fils, matériaux textiles, feuilles et produits similaires ayant des propriétés améliorées Download PDF

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Publication number
EP0120316A2
EP0120316A2 EP84101981A EP84101981A EP0120316A2 EP 0120316 A2 EP0120316 A2 EP 0120316A2 EP 84101981 A EP84101981 A EP 84101981A EP 84101981 A EP84101981 A EP 84101981A EP 0120316 A2 EP0120316 A2 EP 0120316A2
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EP
European Patent Office
Prior art keywords
active
substrate
monomers
substrate according
improved
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP84101981A
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German (de)
English (en)
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EP0120316A3 (fr
Inventor
Gerald Willard Mcneely
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo GmbH
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Akzo GmbH
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Publication date
Application filed by Akzo GmbH filed Critical Akzo GmbH
Publication of EP0120316A2 publication Critical patent/EP0120316A2/fr
Publication of EP0120316A3 publication Critical patent/EP0120316A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation

Definitions

  • the present invention relates to the improvement of certain properties of natural and artificial fibers and threads, in particular those made of polyethylene terephthalate, rayon and nylon, as well as the properties of textile fabrics and foils.
  • the US Defensive disclosure T 100 201 describes a method for applying a polymeric coating agent to polyethylene terephthalate - threads to increase the indigo dyeability of the thread.
  • the coating media according to US Defensive disclosure T 100 201 are polymers which are applied to the substrate as an aqueous dispersion. The substrate is then dried.
  • the polyfunctional monomers of the type used in the present invention are usually used in two ways to arrive at the following natural and artificial product types:
  • One application relates to the use of these monomers without solvents to form a very highly cross-linked polymer.
  • the other relates to the chemical bonding (grafting) of the monomers and the resulting polymers to the substrate. - To achieve both, considerable energy must be used.
  • the present invention is therefore based on the object of making such modified substrates available, for which purpose the problems of known methods have to be overcome.
  • This object is achieved according to the invention by a substrate which has been permanently improved by at least one property, which is characterized in that the substrate has taken up a large number of active chemical compounds, each compound forming a continuous unit which surrounds the said substrate individually and that each of the compounds mentioned one or more suitable active monomers each of which is capable of chemically bonding with its like or a non-active monomer, each active monomer containing at least one active moiety which brings about the improvement of the respective property without impairing the strength properties of said substrate.
  • the active chemical compound can consist of one or more active polyfunctional monomers. These polyfunctional monomers are used in such a way that essentially no extensive crosslinking or grafting occurs. At least two of the process parameters used in the present invention exclude both crosslinking and grafting: use of low energy and dilute monomer solutions. The use of lower energy reduces the possibility of grafting, and the use of dilute monomer solutions increases the likelihood that the monomers will react with themselves rather than with another monomer. The existence of the two aforementioned conditions in the present invention means a considerable enrichment of the technology.
  • the compounds which are used for the first time in the present process can be synthesized according to methods familiar to the person skilled in the art. These are preferably monomers of the formula where A is an active grouping through which the desired improved property can be achieved. Usually polyfunctional monomers are designed to deliver the greatest possible crosslinking potential. The polyfunctional monomers of the present invention have an additional parameter, namely grouping within the molecule, which allows modification of some properties of the substrate to which the monomers are linked. From the wide range of possible active monomers z. B. select those of the following formulas: wherein X is carbon, nitrogen, silicon, phosphorus and sulfur, preferably carbon or nitrogen, R is an alkyl group with 1 to 6 carbon atoms, n is a function of X (i.e. from 2 to 5) and A is the active group.
  • the suitable substrate to be modified according to the invention which - as already mentioned - can be artificial or naturally occurring, can be nylon 6, rayon, cotton, silk, wool, polyester (PET) or polypropylene.
  • PET polyester
  • polypropylene polypropylene
  • an active group which contains a functional portion consisting of phosphorus, antimony, bromine, chlorine or molybdenum.
  • the active chemical compound preferably contains one or more monomers of the formula where A is the active group that mediates the increased hydrophilicity.
  • A is a water-retaining group consisting of sulfate, sulfonate, phosphate, phosphonate or a positively charged quaternary nitrogen.
  • a suitable active chemical compound for achieving increased hydrophilicity particularly preferably contains one or more monomers of the formula (I) with a grouping of the formula wherein each of the substituents R 1 , R 2 and R 3 is an alkyl or aryl radical having 1 to 6 carbon atoms and X acetate, chloride, bromide, sulfonate, phosphate or phosphonate.
  • An active chemical compound which has one or more monomers of the formula is also particularly preferred contains, wherein R and R 1 is an alkyl or aryl radical having 1 to 6 carbon atoms and X acetate, chloride, bromide, sulfate, sulfonate, phosphate or phosphonate.
  • Another preferred active chemical compound is one consisting of one or more substituents of the formula is formed.
  • This monomer dimethyldiallylammonium chloride, is described in US 4,245,992 (product of the National Starch Chemical Corporation, USA; cf. also J. Amer. Chem. Soc 79 (1957), 3128).
  • the suitable substituent preferably contains an organofluorine active monomer.
  • a suitable such monomer is, for example, a fluorinated acrylate.
  • a particularly useful such fluorinated acrylate is the product NUVA F (trade name of H oechst AG).
  • Another suitable fluoroorganic active monomer is if it is used in conjunction with a non-active monomer, for example methylene-bisacrylamide or triallyl-s-triazine-2,4,6-trione.
  • the state of the art with regard to the production of hydrophilic polyester fibers includes the oxalate complex-treated fibers, as can be seen from US Pat. Nos. 4,307,152 and 4,371,485.
  • the production of a usable polyester fiber has been described for the first time, which is characterized in that it has a pore system consisting of micropores and macropores and a moisture absorption (regain) of at least about 2% by weight at 40 ° C. and a relative humidity of 92%.
  • treatment of the polyester fibers described in US 4,307,152 and US 4,371,485 is also preferred, as shown in Example 5 of the present specification.
  • suitable substrate is any natural or synthetic material that contains longer molecular chains.
  • the chains should be long enough so that the polyfunctional monomer of the present invention, after being tied around the chain, cannot simply be stripped off the end of the chain.
  • Most synthetic and natural fibers and filaments have a molecular weight in the range of at least 10,000 to 50,000 and more.
  • Preferred artificial / synthetic fibers and threads are nylon 6, rayon, polyester (PET) and polypropylene.
  • polyester used herein refers to both homo- and copolyesters as are known from the prior art.
  • polyesters are those which are obtained by reacting one or more of the acids listed below or their ester-forming derivatives with one or more dihydric or polyhydric aliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol.
  • Typical acids are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-dicarboxylic acid, decane-dicarboxylic acid.
  • Typical diols or phenols suitable for the production of these homo- and copolyesters are: ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1 , 2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol, 1,4-cyclohexane-dimethanol and bis-phenol A.
  • Polyesters and copolyesters of terephthalic acid especially polyethylene terephthalate (PET).
  • propylene used here means those isotactic propylenes which are normally used in film and fiber production.
  • polyamides used herein includes fibers such as those listed in US Pat. No. 2,163,636, page 4, column 2, lines 20 to 50, the disclosure of which is hereby expressly incorporated by reference. Attention is also drawn to "Encyclopedia of Polymer Science and Technology", New York 1969, HF Mark, NG Gaylord, NM Bikales, vol. 10, pages 392-397, which contains a list of the monomers used in the production of polyamides.
  • active chemical compound used in the present specification denotes a compound which contains at least one active group which mediates the improved desired substrate property.
  • This compound can be a single polyfunctional monomer or consist of two or more chemically combined polyfunctional monomers, at least one of which contains the desired active group.
  • the number of chemically combined polyfunctional monomers in a given suitable substrate should be kept as low as possible, for example between 1 and about 4, so that the desired strength properties of the substrate, for example the modulus of elasticity, elongation properties, etc., are not significantly impaired, when said substituent physically binds to the substrate.
  • A is an active grouping such as - ⁇ N (R) 3 X ⁇ (for dyeability, antistatic and / or hydrophilicity (Hydrophilicity, fire resistance, antistat), CF 3 (CF 2 ) n - (n is 3 to about 18) (anti-soiling and sliding properties)
  • M is metal (Na, K, Li, etc.), R is CH 3 or H.
  • polyfunctional inactive monomers are:
  • any suitable substrate such as any thread, fiber, knitted or woven fabric, film or carpet, can be treated by the method described to give desired results in shape to obtain one or more improved properties.
  • different substrates have to be treated differently, particularly with regard to the physical shape of the substrate.
  • fibers and filaments can be treated with solutions of the active chemical compounds or monomers that form the appropriate compounds during the process.
  • the proportion of monomers in the solution ranges from 1 to at least about 10% by weight (often even up to 50 to 60% by weight), although - as one skilled in the art can easily estimate - deviations from these limits can occur , depending on the substrate used. Because of the solvent aspect already discussed, it is generally desirable to use the most diluted solution possible, which is still sufficient to achieve the desired level of property to be improved.
  • the process can be carried out either by passing the thread through the solution or by applying the solution to the thread by passing the thread over a finish roll that is continuously covered with a solution.
  • Higher temperatures have the advantage of better penetration of the solution into the substrate.
  • extreme temperatures have an adverse effect on the process due to solvent evaporation or even undesirable crosslinking.
  • the person skilled in the art is recommended to start at room temperature (25 ° C.) and gradually increase the treatment temperature to just before the boiling point in order to find the optimal conditions with regard to the desired results.
  • the amount of the substituent or monomer taken up by the thread must be determined by its concentration in the solution to be controlled; as a starting point for a suitable method, a concentration of 1% by weight and then an increase or decrease in the concentration is recommended until the minimum concentration is determined with which the desired property can still be achieved.
  • the treated samples can then be stored for further processing at a later point in time or treated directly afterwards by radiation, infrared or heat, whereby a large number of active chemical compounds are formed which individually coat a segment of the thread or the fiber.
  • An embodiment of the present method using a coil coated with the solution is illustrated in Figure 1.
  • Figure 1 shows an embodiment for the treatment of polyester filament:
  • the untreated polyester filament 2 is treated from spool 1 via a spool 3 with the active solution 5 in container 4.
  • the treated moist filament 6 is irradiated from a UV or EB source 7.
  • the treated dry filament is then taken up by an end spool 9.
  • the material can either be passed through a solution of the monomers or sprayed with such a solution.
  • the treated samples are then either stored or treated immediately afterwards to form a variety of chemically active compounds.
  • carpets can be sprayed with solutions and then treated in the same way as threads or fabrics.
  • the substrate can be preheated or heated after application of the solution.
  • the same restrictions apply as previously discussed. So be careful: Excess heat will unnecessarily result in inadequate solvent evaporation and can lead to unwanted cross-linking.
  • Better penetration of the solution can also be achieved by using commercially available swelling agents (e.g. trifluoroethanol or phenols for polyester, xylenes for polypropylene, benzyl alcohol for nylon 6 etc.) (see also MJ Schuler, "J. Textile Research", 27 , 352 (1957); “Encyclopedia of Polymer Science and Technology", Vol. 5, 372 (1966); T. Vickerstaff, "The Physical Chemistry of Dyeing", London 1954, 489-491; HU Schmidlin, "Preparation and Dyeing of Synthetic Fibers ", New York 1963, 254-258).
  • swelling agents e.g. trifluoroethanol or phenols for polyester, xylenes for polypropylene, benzyl alcohol for nylon 6 etc
  • the present process provides an irradiation or heating step in which the solvent in the amount present is normally evaporated off and a dry substrate is obtained. All radiation procedures were performed on an electron beam (Energy Scienees, Ind., 8 Gill Street, Woburn, Massachusetts 01801) or a Deco-Ray LTM ultraviolet laboratory system (Fusion Systems Corporation, 12140 Parklawn Drive, Rockville, Maryland 20852). As will be readily appreciated by those skilled in the art, the treatment stage in which the solution is applied must be distinguished from the final stage in which the substrate must inevitably be irradiated or heated in order to obtain a dry substrate.
  • This example shows a process with which a nylon 6 thread with increased dirt resistance and color fastness is obtained due to reduced surface tension and increased water repellency.
  • a 2600 denier nylon 6 thread was treated with the following solution:
  • This example shows a process for making a nylon 6 thread with improved antistatic properties due to reduced resistivity. 2600 denier nylon 6 threads were treated with the following solutions:
  • This example describes a process for the production of a polyester thread (AEC) with improved indigo dyeability.
  • a 320 denier polyester thread was treated with the following solution:
  • the treated sample was UV irradiated as in Example 3 and then knitted to a tube.
  • the knitted tube was extracted with boiling water for 3 hours and then subjected to chlorine analysis and indigo staining. The results of these tests are shown in the following table:
  • This example shows a process for producing a polyester thread with increased moisture absorption (regain).
  • a 420 denier polyester thread containing 10% by weight of K3Al (e204) 2 * was treated with the following solution:
  • the treated sample was EB-irradiated at a dose of 5 Mrad and then subjected to a moisture absorption test (regain) together with a hydrophilic polyester (PET) as a comparison sample, as is discussed in "AEC standard procedure No. 20".
  • PET hydrophilic polyester
  • the film was washed with 300 ml of an equal parts methanol / water mixture and then in 250 ml of acetone. IR analysis showed that the film contained amide carbonyl groups. A change in hydrophilicity was demonstrated with water flow measurements. A control film gave no water flow at a pressure below 2.8 bar and the grafted film had a water flow of 1 ml / min at 0.7 bar.

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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP84101981A 1983-03-01 1984-02-24 Fibres, fils, matériaux textiles, feuilles et produits similaires ayant des propriétés améliorées Withdrawn EP0120316A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46906683A 1983-03-01 1983-03-01
US469066 1983-03-01

Publications (2)

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EP0120316A2 true EP0120316A2 (fr) 1984-10-03
EP0120316A3 EP0120316A3 (fr) 1987-03-04

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EP84101981A Withdrawn EP0120316A3 (fr) 1983-03-01 1984-02-24 Fibres, fils, matériaux textiles, feuilles et produits similaires ayant des propriétés améliorées

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EP (1) EP0120316A3 (fr)
JP (1) JPS59168178A (fr)
ES (1) ES8606552A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064662A1 (fr) * 1998-06-10 1999-12-16 The Secretary Of State For Defence Revetements de surfaces
CN101768788B (zh) * 2010-02-05 2011-06-15 浙江古纤道新材料股份有限公司 一种液相增粘熔体直纺涤纶工业长丝生产工艺
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL232818A (fr) * 1957-10-31 1900-01-01
US2959565A (en) * 1958-01-29 1960-11-08 Dow Chemical Co Compositions comprising graft copolymers of certain monomeric polyglycol esters of acrylates and methacrylates on superpolyamide substrates
NL244572A (fr) * 1959-04-01 1900-01-01
US3190925A (en) * 1962-06-25 1965-06-22 Dow Chemical Co Monomeric alkenyl benzyl polyglycol ethers
GB1160676A (en) * 1965-10-07 1969-08-06 Deering Milliken Res Corp Improvements relating to Cellulosic Textiles
JPS5598915A (en) * 1979-01-16 1980-07-28 Japan Exlan Co Ltd Production of fiber swelling with water
FR2471438A1 (fr) * 1979-12-10 1981-06-19 Energy Sciences Inc Procede de greffage d'un additif ignifugeant sur des etoffes, fibres et autres matieres inflammables

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064662A1 (fr) * 1998-06-10 1999-12-16 The Secretary Of State For Defence Revetements de surfaces
GB2358635B (en) * 1998-06-10 2002-10-02 Secr Defence Surface coatings
CN101768788B (zh) * 2010-02-05 2011-06-15 浙江古纤道新材料股份有限公司 一种液相增粘熔体直纺涤纶工业长丝生产工艺
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods

Also Published As

Publication number Publication date
JPS59168178A (ja) 1984-09-21
ES530104A0 (es) 1986-04-01
ES8606552A1 (es) 1986-04-01
EP0120316A3 (fr) 1987-03-04

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