CN1514898A - Modification of fabric fibers - Google Patents
Modification of fabric fibers Download PDFInfo
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- CN1514898A CN1514898A CNA028116941A CN02811694A CN1514898A CN 1514898 A CN1514898 A CN 1514898A CN A028116941 A CNA028116941 A CN A028116941A CN 02811694 A CN02811694 A CN 02811694A CN 1514898 A CN1514898 A CN 1514898A
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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
- 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
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/54—Substances with reactive groups together with crosslinking agents
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
This invention is directed towards fibers of fabric or other fibrous substrates coated with amine-containing polymers. These polymers impart durable anti-microbial activity, renewable control of certain odors, and the capacity to bind certain materials to the substrate surface.
Description
Technical field
The present invention relates to be coated with fabric or other fibre substrate of amine-containing polymer.These polymer are given fabric face durable antimicrobial activity, some smell of recoverable control and some material are adhered to ability on the fabric face.
Background technology
Only usually lack required character by natural (for example cotton, wool, silk) or synthetic (for example polyester, nylon, acrylic acid) fibrous fabric.In textile industry, in fabric, add a small amount of different chemical reagent component usually to give required performance; Usually these processing are called " arrangement ".Such chemical intensifier comprises dyestuff, fluorescent whitening agent, softener, waterproofing agent, waterproof/finish, pest repellant, antimicrobial and/or antimycotic finishing agent, antistatic finishing agent and hydrophilic finishing agent.
Simultaneously, durability is required performance, and all is a great challenge for any arrangement.Even it has slight volatile molecule finally also can evaporate; Sunlight and air will slowly make other molecular breakdown.Cleaning method such as washing, dry-cleaning and detergent washing are the most great challenges for the fabric finishing agent durability.After only cleaning several times, many finishing agents will remove from fabric.
Taked the whole bag of tricks that durable finish is provided.A kind of method is that the difficult chemical reagent (being typically polymer) that dissolves and wash away of post precipitation is deposited on the fabric.Perhaps, the reactive ingredients of finishing agent can be embedded in the laminar films that is coated on the fabric; The method usually can make reactive ingredients slowly be discharged in the fabric on every side.Yet when it only is when depositing on the fiber surface, the washing agent of conventional cleaning method and mechanical agitation are usually removed polymer or laminar films at last.
When for example in cotton, flax, wool or silk, when fabric fibre contained effective reactive group, finishing agent can be attached on the fabric by covalent chemical bond.This method is very effective, but is limited to the kind of fiber and finishing agent.An artificial fibre (for example regenerated cellulose, artificial silk or some non-synthesizing polyester) and a shortcoming of synthetic fiber (for example acrylic acid, Lycra, polyester and nylon) are not have effective reactive group substantially; Most such groups exhaust in forming main polymer chain.Like this, be difficult to by covalent bonding a large amount of finishing agents is attached on the synthetic fiber, therefore the effective ways of this acquisition finishing agent durability are of no use to synthetic fiber.
In polymer-coated, it is desirable to provide a kind of method of parcel fabric fibre, particularly synthetic fiber.In this way, fiber will provide support structure for polymer shell, and improve polymer to the durability of conventional cleaning method as washing and dry-cleaning.Polymer will provide required characteristic for fabric, be included in potentially the reactive group that can be used as further textile finishing binding site is provided on the fiber surface." desirable characteristics " that some can be given by finishing agent hereinafter will be described.
The US 6,187,856 that authorizes people such as Incorvia has instructed and has used the crosslinked resin that is formed for the alcohol and cross linking agent by polyamidoamines amine and polychlorostyrene, with the durable film of formation on fabric.Claim that the resin of this patent will give lasting antistatic property for fabric.In this patent, durability is defined as the performance that treated fabric is immersed in 80 ℃ the hot water antistatic property after two 20 minute periods.
Antimicrobial finish is that many textile application all extremely need.They can be applied to need in the occasion of antibiotic condition as on the fabric that uses in the hospital.They also can be used for the fabric that old fabric or following occasion are used: commercial food product, medical space and other make the people be exposed to the zone of infective bacterial most probably.
Have only a few class Antimicrobe compounds.Because great majority are micromolecule that easy evaporation maybe can be flushed away, so durability is a great problem for them.And many Antimicrobe compounds all demonstrate toxicity to the people.It is desirable to invent a kind of lasting, harmless to mankind antimicrobial fabric finishing agent.
Determined (50 amino acid or still less) cytotoxic polypeptide (people such as Maloy, Biopolymers (Peptide Science) 37:105-122 (1995)) of many weak points.They have arginine and the high denominator of lysine residue content, and carry clean positive charge under physiological pH.The mechanism of toxicity likes the cytolysis of mediating by peptide and cell membrane static coordination well.
The US 5,300,287 that authorizes Park has instructed polymine, particularly derives with polyethylene glycol, has antimicrobial and graft polymers antifungal activity with formation.These polymer are particularly suitable for using in ophthalmology goods and contact lens care solution.
The US 6,034,129 that authorizes people such as Mandeville has instructed the use cationic polymer to handle bacterial infection in the mammal (specifically human).The polymer of describing in this patent has amino or the ammonium that side is hung on main polymer chain.
For the clothing fabric, can eliminate or significantly reduce the smelly and smelly ability of pin of the armpit (body) of stench is the characteristic that needs.The chemical constituent of underarm odor is the waste by-product by some bacterium of the secretion keeping of human sweat gland.The bacterium of these kinds is called lipophilicity diphtheroid (lipophilic diptheroids).Determined in body odor that 36 molecules with potential foul smell (see Preti, people such as G., J.Chem.Ecology, 1991,17,1469; Preti, people such as G., J.Chem.Ecology, 1992,18,1039; Preti, people such as G., J.Chem.Ecology, 1996,22,237; Proc.Nat.Acad.Sci.USA, 1996,93,6626).All these is an organic acid, and the main source of stink has been defined as trans-3-methyl-2-hexenoic acid.The chemical constituent that pin is smelly has similar source; They are refuses of bacterium brevibacterium epidermidis (brevidium epidermis).These molecules also are organic acids, and most important component is isovaleric acid (seeing Kanda, people such as F., Brit.J.ofDermatology, 1990,122,771).It is desirable on fabric, to have the durable finishes that to eliminate or significantly to reduce the body odor of stench.A kind of method is to comprise the sterilization finishing agent.Yet these methods can not be killed the bacterium that survives on the skin, therefore still can produce stink.Another kind method is to use to absorb and produces underarm odor and the smelly stench organic acid finishing agent of pin, and undesirable like this organic acid volatilization concentration is lower than the threshold value of detectability.The utmost point it is desirable to can be by the standard cleaning method this finishing agent of absorptive capacity that recharges.
The US 4,244,059 that authorizes Pflaumer has instructed and has used water-soluble amine-containing polymer Tydex-12 (Dow Chemical Co.) as " odour adsorbent compound ".Tydex-12 is coated on the fabric soft, ventilative, that is made up of cellulose fibre, then, this treated fabric of use in making close-fitting type clothes.Treated fabric is used for absorbing the stink that sends from vagina and peripheral region.This patent is about the claim of durability, thereby also do not take measures to provide the durability of polymer for fabric at common cleaning method in as the process of washing.
The WO97/34040 that authorizes people such as Koizumi instructed use polyamine as the coating of acrylic fiber to produce deodorization fiber.In this patent, the wet gel acrylic fiber that contains acid gene is contacted with " nitrilo compound ", carry out the stoichiometry adjustment and make that amine groups is excessive.The root of the chances are the durability of the electrostatic interaction between amine and the acid groups.This fiber has been wet spinning, and does not have drying in advance.After touching amines, " at wet heat condition, 100-180 ℃ " be the fiber of heating coating down.Can remove acid stink by the fibre that these fibers constitute.
Summary of the invention
The present invention relates to be used for the durable finishes of fabric and other fibre substrate.The reactive component of finishing agent is the amine-containing polymer with reactive group.This polymer is crosslinked on the matrix fiber surface, and forms resinous coat soft, anti-cleaning method.The reactive group of amine-containing polymer can be an amine, but is not only limited to this functional group.
The invention still further relates to fiber with amine-containing polymer coating processing of the present invention; Yarn; Weaving, braiding or bondedfibre fabric and textiles; And finished product (being included in the term " fibre substrate " herein).
The fibre substrate of handling with finishing agent described herein has undiscovered performance in natural fabric, comprises antimicrobial properties and/or elimination or significantly reduces the most undesirable component in the body odor of stench.When being coated to synthetic textiles such as polyester or nylon, reactive group of the present invention provides binding site and adds on the amine-containing polymer of wash resistant process (before applying, simultaneously or in the technology of back) so that other has reactive finishing agent.Can be by forming ionic bond with reactive group of the present invention and/or amido or covalent bond improves durability.Polymer coating also provides new opportunity for textile dyeing.For example, chemically-reactive dyes can form covalent bond with amine-containing polymer, therefore is used for dyed synthetic fiber.
Detailed Description Of The Invention
Herein with appended claims in " a " and " an " that use mean one or more, except as otherwise noted.
Term used herein " durable " or " durability " have been described the fibre substrate of arrangement, are wherein repeatedly still observing the desired properties that finishing agent is given matrix after washing or the dry-cleaning.
Concerning this specification and subsidiary claims, term " amine-containing polymer " specifically refers to contain and is positioned at the polymer that main polymer chain or side are hung on the amido on the main polymer chain.Concerning this specification, term " amido " refers to primary, the second month in a season and/or tertiary amine groups.This polymer also can contain the quaternary amine base, but comprise the quaternary amine base and do not have primary, the second month in a season or tertiary amine groups be not enough to regard this polymer as describe " amine-containing polymer " herein.Amine-containing polymer also contains reactive group; These reactive groups can be but not be only limited to amido.The example of another kind of reactive group comprises but is not only limited to hydroxyl, mercaptan and carboxylic acid.
Amine-containing polymer can be homopolymers, copolymer or trimer, and it can be derived from natural or prepare by synthetic.The example that is derived from natural amine-containing polymer comprises polysaccharide that contains amine and the polypeptide that contains amine.In preferred embodiments, this natural polymer is a chitosan.The example of synthetic amine-containing polymer comprises polymine (PEI) and PEI derivative, polyvinylamine, polydiene propyl group amine, polyallylamine, diallylamine and the copolymer of allylamine, the copolymer that contains diallylamine and/or allylamine and trimer, by the polyamine monomer with have the condensation polymer that the monomer of two or more reactive amine groups forms.Other example of amine-containing polymer is the polyacrylate be made up of the acrylate monomer of amino-contained wholly or in part, the polymethacrylates of being made up of the methacrylate monomers of amino-contained wholly or in part and copolymer or the trimer of being made up of acrylate, methacrylate and/or other vinyl monomer, wherein in this polymer, at least some and may all monomers amino-containeds all.
The preferred embodiment of the invention comprises synthetic polymer P EI and PEI derivative, polyvinylamine and contains diallylamine or the polymer of allylamine.Can be with containing such as halohydrin, epoxides, organic acid, α, the molecule of the reactive group that β-unsaturated organic acid and carbonyl the are such PEI that derives.PEI polymer and the PEI polymer of deriving can be buied from Nippon Shokubai and BASF.Preferred polymer from BASF buy, the PEI of the chloropropylene oxide grafting of commodity LupasolSC-86X by name.
Term used herein " crosslinking agent " refers to the molecule of the functional group of the reactive group Cheng Jian that contains two or more and amine-containing polymer.Crosslinking agent combines amine-containing polymer, thereby forms the coating of polymer film around fiber.The fiber that contains reactive functional groups also can react with crosslinking agent, thereby the amine-containing polymer coating is directly sticked on the fiber.
In one embodiment, the amido of amine-containing polymer also is the reactive group that is used to form the non-durable fibers coating.In this embodiment, it is particularly preferred containing the uncle and/or the polymer of secondary amine.The those of ordinary skill of chemical field will recognize that primary amine and secondary amine have the versatility more much bigger than tertiary amine at Cheng Jianzhong, thereby widen the kind of potential cross-linking agent.In order to form durable coating, reactive group in the crosslinking agent should exist with sufficient amount, but preferably the amido with respect to polymer exists with substoichiometric amount, particularly when when making the second layer finishing agent of back durable with amine-containing polymer reaction.In this embodiment, the reactivity that it is desirable to crosslinking agent especially has significant selectivity to amine, thereby make crosslinking agent react effectively polymer is combined.In one embodiment, desirable (but and not requiring) is to participate in basicity basic no change after reaction of the nitrogen-atoms of cross-linking reaction.Concrete amine reactive group comprises alkyl halide, isothiocyanates, isocyanates, acyl azide, N-hydroxy-succinamide ester, sulfonic acid chloride, aldehyde, dialdehyde, epoxides, ethylene oxide, carbonic acid ester, arylating agent, imino esters, carbodiimide, acid anhydrides and halohydrin.In a preferred embodiment, crosslinking agent contains halohydrin or epoxide reaction group.The example of these crosslinking agents is 1,3-two chloro-2-propyl alcohol and 1,4-butanediol diglycidyl ether (Sigma-Aldrich company).
In another embodiment, amine-containing polymer also contains non-amine reactive group.When the amido of polymer was tertiary amine groups all or almost all, it was valuable especially having non-amine reactive group.The example of the non-amine reactive group of Shi Yonging comprises hydroxyl, mercaptan and carboxylic acid in the present invention.In preferred embodiments, reactive group is a hydroxyl.It is desirable to especially, cross-linking reaction does not influence the basicity of amine in the film that obtains.Not necessarily, can comprise that catalyst is crosslinked to promote.Reactive hydroxyl functional group comprises epoxides, halohydrin, ethylene oxide, carbonyl dimidazoles, N, N '-two succinimidyl carbonate or N-hydroxy-succinamide base chloro-formate, alkyl halide, isocyanates and N-methylolurea.Mercapto and halo acetyl and alkyl halide derivative, maleimide, aziridine, acryloyl derivative, arylating agent and mercaptan-disulfide exchange reagents such as pyridyl disulfide, disulfide reducing agent and 5-sulfo--2-nitrobenzoyl acid reaction.Reactive carboxylate group comprises diazoparaffins and diazonium acetyl compound, oxazoline, carbonyl dimidazoles, carbodiimide and N-methylolurea.Preferred cross-linking agents is di-epoxide (a Sigma-Aldrich company), (PatCoRez P-53 is BFGoodrich) with block polyisocyanate such as Repearl MF (Mitsubishi Chemical company) for N-methylolurea such as dihydroxymethyl dihydroxy ethylidene-urea (DMDHEU).
The finishing agent that is coated on the fibre substrate is a kind of solution, and this solution comprises amine-containing polymer, crosslinking agent and volatile solvent at least.It is desirable to, polymer and crosslinking agent dissolve in the solvent.Particularly preferred solvent is a water.Pad (pad) solution and preferably contain about 0.01-75 weight %, more preferably about 0.05-50 weight % most preferably is the amine-containing polymer of about 0.1-40 weight %.Leach mill solution preferably contains about 0.001-40 weight %, more preferably from about 0.01-30 weight %, the most preferably from about crosslinking agent of 0.05-20 weight %.Finish solution also can comprise other component as described below.
In special embodiment of the present invention, be placed into handle in the body lotion before, amine-containing polymer part and crosslinking agent reaction, for example have only substantially in two or more reactive groups of crosslinking agent one with the amine-containing polymer pre-reaction.Then, the graft polymers that obtains joined handle in the body lotion, and be coated on the fabric, after this, solidify this fabric to finish the reaction with crosslinking agent.Graft polymers can be unique component of handling body lotion; Perhaps can comprise other component such as extra crosslinking agent and wetting agent.
The reaction of amine-containing polymer and some crosslinking agent functional group such as halohydrin causes forming the inorganic acid that reduces finishing agent pH value, and can make the slack-off and crosslinking degree reduction of cross-linked speed.In order to control this adverse effect, can in finish solution, add buffer.Buffer is weak acid or weak base, they can make the solution that contains them remain on this buffer pKa ± the 1pH value in.One of ordinary skill in the art will appreciate that best cushioning liquid by etc. the buffer of molar part and its corresponding conjugate acid or alkali forms, the latter is usually by adding the formation of strong acid or highly basic.Can be at Lange ' s Hankbook of Chemistry, the 14th edition, J.A.Dean edits, McGraw-Hill, Inc., the 8th chapter is found enumerating of buffer in the 103-112 page or leaf.If use, should select buffer, make the pKa of this buffer within the optimal pH scope of reaction.This pH value scope depends on the type of the reactive group of amine-containing polymer and crosslinking agent.Also buffer must be selected so that it does not react with crosslinking agent or amine-containing polymer.The amount of buffer should be a bit larger tham the theoretical total amount of the equimolar acid that is produced by the crosslinking agent complete reaction.
Finish solution can also comprise other additive.For example, amido is easy to oxidation, and its byproduct usually is a yellowish-brown.In finish solution, add antioxidant can make storing state under and apply finishing agent and on fabric the degree of oxidation during curing all reduce to minimum.Preferred anti-oxidants of the present invention is a phosphoric acid.Can comprise fluorescent whitening agent (for example Uvitex product of the Leucophor product of Cariant company or Ciba company) in the finisher solution.Also can comprise brightening agent such as sodium tetraborate in the solution.Finisher solution can also contain wetting agent, is evenly distributed on the fiber with auxiliary finishing agent as WetAidNRW (BFGoodrich company).When the fibrous material hydrophobic, this is useful especially.Can on demand other additive be joined in this solution.
Can be exposed in the finisher solution by making matrix, flow and pad and finishing agent is coated on the fibre substrate with method as known in the art such as immersion, injection, dipping, fluid.Then, the fibre substrate of heating exposure is to remove volatile solvent and to quicken polymer and the reaction of crosslinking agent.Perhaps, can fiber or yarn be exposed in the finisher solution by soaking, spray or flooding.Behind the finishing agent cured in place, fabric can be compiled or be made into to fiber or yarn.
Can under any temperature below the boiling point above freezing of solvent, finisher solution be coated on the fibre substrate.In embodiment of the present invention, application temperature is preferably 5-90 ℃, more preferably 10-50 ℃, most preferably is room temperature.Treated fiber should solidify under the temperature that is high enough to make shell to form in the very short time, is preferably less than 5 minutes more preferably 1 minute or shorter.In embodiment of the present invention, solidification temperature is preferably 100-180 ℃, more preferably 110-140 ℃.
The invention still further relates to the fibre substrate of handling with above-mentioned finishing agent.The matrix of Chu Liing will have undiscovered performance in undressed matrix like this.These performances comprise antimicrobial properties and can absorb the organic acid ability of stench by the acid and the acid-base reaction of the amido of finishing agent.Under all or part of situation about being made of the synthetic fiber of inertia of matrix, treated fiber provides reactive group on their surface.Further processing with second finishing agent that contains the group that reacts with modified fibre will make second finishing agent have durability.The example of required durable second finishing agent comprises dyestuff, softener, waterproofing agent, waterproof/finish, pest repellant, antimicrobial and/or antimycotic finishing agent, antistatic finishing agent and hydrophilic finish agent.
In one embodiment of the invention, treated fibre substrate has antimicrobial performance.Stop bacterium, mould or conk or active fabric and other fibre substrate that kills them to be wanted very much, particularly the fabric in biological pollution may be the place of the infection sources, as in hospital and food preparation place.Verified, finish coating of the present invention provides antimicrobial performance durable, non-elimination for treated fabric.Though not bound by theory, it is believed that the effect of finishing agent is owing to the cationic charge of polymer.The cells of microorganisms wall mainly is made of electronegative phosphate lipid bilayer.In theory, the static coordination of this lipid bilayer and finishing agent polymer has destroyed cell membrane and kill microorganisms.
Another embodiment of the invention is preparation absorption organic acid and the treated fibre substrate of removing its stink, and it gives the ability that undesirable body odor was eliminated or significantly reduced to this type of matrix.In case of necessity, can resupply the fabric odor absorption ability by the washing methods of routine.The molecular source of undesirable body odor mainly is the refuse of the bacterium of class lipophilicity diphtheroid by name.This bacterium lives on the human skin surface, mainly digests eccrine secretion.The malodorous waste of lipophilicity diphtheroid is an organic acid, and most important component is 3-methyl-2-hexenoic acid.Usually, also has an extremely undesirable stink even think that VFA concentration is extremely low.The odor absorption ability of treated fibre substrate is derived from the basicity of the amido of finishing agent.The free amino reaction of acid and amine-containing polymer, thus nonvolatile ionic complex formed.The degree that this ion complexation takes place depends on the relative intensity of acid and alkali.Under situation of the present invention, response bias forms ionic complex so far, finds promptly to have only in 10,000 acid molecules that to have only 1 in 1 to 1,000,000 acid molecule be volatile form nonionic, possible.Therefore, as long as in treated fabric, there is a unreacted amido, the volatilization organic acid concentration around the treated fabric will be reduced to can not detect or almost detect less than value.
It is to resupply the fibre substrate odor absorption ability that the present invention compares conventional advantage of inhaling smelly material such as activated carbon.Because amine is weak base, so that matrix is exposed to the pH value for this alkali pKb or be higher than in the aqueous solution of this alkali pKb and will make most of amine complex slough proton, and cause amine-acid complex to separate.In liquid detergent, the stench organic acid of conjugate base form can be flushed away, and stays amido freely on fiber surface.10 pH is higher than the pKb of most of amine, typically, and cloth-washing detergent solution such as Tide
Have this pH value or higher pH value.Therefore, Chang Gui washing methods is enough to revest the fabric odor absorption ability.
Another embodiment of the invention is the fiber surface that preparation has reactive amino, and these amidos can be participated in other finishing agent is bonded on the fibre substrate in durable mode.When fiber was made up of the polymer that does not have a lot of reactive groups, as in polyester and nylon, this was useful especially.There is reactive group in the fiber of handling with amine-containing polymer finishing agent of the present invention on their surface.The further processing of carrying out with second finishing agent that contains the group that reacts with modified fibre will make second finishing agent have durability.The example of desirable durable second finishing agent comprises dyestuff, fluorescent whitening agent, softening agent, waterproofing agent, waterproof/finish, pest repellant, antimicrobial and/or antimycotic finishing agent, antistatic finishing agent and hydrophilic finish agent.
The reactive group of the amine-containing polymer that depends on of the essence of the reactive functional groups of second finishing agent as mentioned above.The example of reactive amine group comprises isothiocyanates, isocyanates, acyl azide, N-hydroxy-succinamide ester, sulfonic acid chloride, aldehyde, dialdehyde, epoxides, ethylene oxide, carbonic acid ester, arylating agent, imino esters, carbodiimide, acid anhydrides and halohydrin.Reactive hydroxyl functional group comprises epoxides, halohydrin, ethylene oxide, carbonyl dimidazoles, N, N '-two succinimidyl carbonate or N-hydroxy-succinamide base chloro-formate, alkyl halide, isocyanates and N-methylolurea.Mercapto and halo acetyl and alkyl halide derivative, maleimide, aziridine, acryloyl derivative, arylating agent and mercaptan-disulfide exchange reagents such as pyridyl disulfide, disulfide reducing agent and 5-sulfo--2-nitrobenzoyl acid reaction.Reactive carboxylate group comprises diazoparaffins and diazonium acetyl compound, carbonyl dimidazoles, carbodiimide and N-methylolurea.
The purpose of following examples just is used for explanation.Those of ordinary skills can take into account other embodiment, and all these embodiments all are considered to a part of the present invention.
Embodiment
Embodiment 1
Preparing the pH value by following steps is 9.0 10% polymine (PEI, molecular weight 70,000, Nippon Shokubai) and 5%1,100.0 gram solution of 3-dichloro 2-propyl alcohol (DCP, AldrichChemical company): mix 33.3 gram PEI (30% solution) and 50.0 gram water, regulate the pH value with hydrochloric acid (VWR), other adds water makes quality reach 95.0 grams, adds 5.0 gram DCP then.Microdenier polyester textile cloth specimen undyed, weaving is impregnated in this solution,, in 121 ℃ forced ventilation baking oven, solidified 5 minutes by padding roller or " padding " processing.It is in 9.0 the water that the contrast cloth specimen (C-1) of identical fabric is immersed pH value, is among 9.0 the 10%PEI with second contrast cloth specimen (C-2) the immersion pH value.Pad all contrast cloth specimens, in 121 ℃ forced ventilation baking oven, solidified 5 minutes then.All cloth specimens are cut into four parts.With one group 1/4 part of the rinsing 20 minutes individually of cool running water; This group is called zero (0) family herein and washes (HL) sample.According to the method 124-1996 of U.S. fabric chemist who reports for work in the AATCC technical manual (1999) and colourist (AATCC) association, machine-wash remaining three groups 1/4 part 5,10 or 20 times.When finishing when washing, all 1/4 part is cut in half.One group of moiety dyes as follows, and another group moiety is used to inhale smelly analysis.
With sample cloth specimen to be dyeed place 0.1% dyestuff acid red 37 the aqueous solution (20: 1, solution: article than) in 30 minutes.When dyeing is finished, from dye bath, take out sample, and with the rinsing 1 minute individually of cool running water.Note coloring degree and be recorded among Fig. 1 under " color " column headings.Untreated polyester does not almost have or does not have affinity to ACID DYES, and PEI has strong affinity to ACID DYES, so this test is the outstanding indication that PEI exists.
Carry out the stink analysis as follows: one 0.01% butyric acid solution is put on the every cloth specimen, makes this droplet drying then.Then, the judge group membership hears every cloth specimen, and stink is chosen as strong, weak or not obvious.Judge's gross impressions are recorded in the table 1 under " stink " column headings.
Table 1
| Sample | ????????0HL | ???????5HL | ????????10HL | ???????20HL | ||||
| Color | Stink | Color | Stink | Color | Stink | Color | Stink | |
| Handle | Dark red | Do not have | Red | Do not have | Red | Do not have | Pale red | A little less than |
| ????C-1 | Red | By force | In vain | By force | In vain | By force | In vain | By force |
| ????C-2 | Dark red | Do not have | Light pink | By force | In vain | By force | In vain | By force |
Embodiment 2
24.0 gram PEI, 0.3 restrain WetAid NRW and 2400.0 gram distilled water prepare 4%PEI (BASF by mixing in beaker, Mn=60,000), 3%1, the solution of 4-butanediol diglycidyl ether (Sigma-Aldrich company) and 0.1%WetAidNRW (BFGoodrich).With 85% phosphoric acid (Baker) the pH value of this solution is adjusted to 9.0.Add enough water so that gross mass reaches 291.0 grams, add 9.0 grams 1 subsequently, the 4-butanediol diglycidyl ether.Stir this prescription (prescription A) then fully.
Prescription B is that pH value is the aqueous solution (300.0 restrain) of 9.0 4%PEI and 0.1%WetAid.
Prescription C is 3%1, the aqueous solution of 4-butanediol diglycidyl ether and 0.1%WetAid (300.0 gram).
Prescription D is the aqueous solution (300.0 restrain) that the pH value is adjusted to 9.0 0.1%WetAid with NaOH (Aldrich).
The cloth specimen of three polyester textile and a kind of COTTON FABRIC is immersed in each solution.Then, pad these cloth specimens to evenly wet absorption, dry under 157 ℃ then, the time is after 15 seconds behind the fabric drying.Wash these samples 30 times according to AATCC method 124-1996 then.Preceding from washing, the washing once with 30 times after fabric downcut swatch.As described in embodiment 1, every swatch is inhaled olfactory test.
The cloth specimen of handling with prescription A is also inhaled smelly after washing 30 times, and that other treated sample is not just inhaled is smelly.
Embodiment 3
Prepare 5% ethyoxyl PEI (BASF), 0.1%WetAid NRW (BFGoodrich) and 3%1 by mixing 67.5 gram ethoxylation PEI, 0.5 gram WetAid and 417.0 gram water, 500.0 gram solution of 4-butanediol diglycidyl ether (Sigma-Aldrich company), A promptly fills a prescription.Add 15.0 grams 1 then, the 4-butanediol diglycidyl ether, and fully stir this solution.
Prescription B is by 500.0 gram 0.1%WetAid solution compositions.
Cut the cotton/Lycra fabric cloth specimen of three woven polyester, COTTON FABRIC and 90/10, and immerse in two prescriptions one.Then, pad these cloth specimens to evenly wet absorption, dry under 157 ℃ then, the time is after 15 seconds behind the fabric drying.Wash these samples 30 times according to AATCC method 124-1996 then.Preceding from washing, the washing once with 30 times after fabric downcut swatch.
Use 0.01% butyric acid that the cloth specimen that washs 30 times is inhaled olfactory test.The judge group membership compares the stink and the untreated tester of treated sample.The value of determining tester is 3.If on the cloth specimen of handling, do not detect stink, determine that then its value is 0.With respect to tester, with any on the treated fabric can detected butyric acid stink divided rank 1-3.Also make house wash 30 times swatch dyeing according to the method for describing among the embodiment 1.
The results are shown in the table 2 of dyeing and sense of smell test.The polyester cloth specimen is defined as PET#, and cotton is COT, and cotton/Lycra mixture is C/L.Suffix T represents to handle with prescription A, and suffix U represents to handle with prescription B.
Table 2
| Sample number judge 1 judge 2 judges 3 mean standard deviations dyeing color and luster | ||||
| ??PET1-T ??PET1-U ??PET2-T ??PET2-U ??PET3-T ??PET3-U ??COT-T ??COT-U ??C/L-T ??C/L-U | ???0????0????0 ???3????3????3 ???1????0????0 ???3????3????3 ???0????0????0 ???3????3????3 ???0????0????0 ???3????3????3 ???0????0????1 ???0????3????3 | ????0.00 ????3.00 ????0.33 ????3.00 ????0.00 ????3.00 ????0.00 ????3.00 ????0.33 ????2.00 | ????0.00 ????0.00 ????0.58 ????0.00 ????0.00 ????0.00 ????0.00 ????0.00 ????0.58 ????1.73 | Whitewash whitewash whitewash rouge and powder rouge and powder |
Embodiment 4
100.0 gram 30%PEI (Nippon Shokunai, Mn=70,000) are mixed with 7.8 gram glycidols (Sigma-Aldrich).Glycidol was at room temperature reacted 1.5 hours with PEI.Suppose polymine and glycidol complete reaction.Hereinafter, the polymine with the product glycidol grafting that obtains is called PEI-g20.Use PEI-g20 and do not carry out further purifying with the form of 35% aqueous solution.
Prepare a series of pad bath formula of liquid: all use hydrochloric acid (VWR) to be adjusted to pH 3.5 all prescriptions.Prescription A is made up of water.(BFGoodrich) form by the DMDHEU resin by 10%PatCoRez P-53 for prescription B.Prescription C is made up of 12.6%PEI-g20.Prescription D is made up of 10%PatCoRezP-53 and 12.6%PEI-g20.For each prescription, immerse two cotton samples, pad then and dried/cured 3 minutes.Wash the piece of cloth sample 5 times of each prescription then according to AATCC method 124-1996.
Then, test the antimicrobial acivity of these cloth specimens according to AATCC test method 100.Outcome record is in table 3.The prescription that sample number into spectrum immerses corresponding to sample.There is too many bacterium colony in term " TMTC " expression so that can't counts.It should be noted that is in washes under 0 and 5 time (sample C and D), and all moment is killed bacteria tested to PEI-g20 substantially.DMDHEU resin among the PatCoRezP-53 also has antimicrobial acivity, may be because its slow release formaldehyde (sample B) when decomposing; Yet, effect slowly many.Untreated tester (sample A) does not have antimicrobial acivity.
Table 3
| Sample number into spectrum #HLs bacterium colony # | |
| % killed in 0 hour 24 hours | |
| A?????????0????????????????????????????????????????????????????TMTC???TMTC???0％ ??????????5????????????????????????????????????????????????????1589???TMTC???0％ B?????????0????????????????????????????????????????????????????TMTC???0??????100％ ??????????5????????????????????????????????????????????????????TMTC???0??????100％ C?????????0????????????????????????????????????????????????????0??????0??????100％ ??????????5????????????????????????????????????????????????????423????0??????100％ D?????????0????????????????????????????????????????????????????428????0??????100％ ??????????5????????????????????????????????????????????????????0??????0??????100％ | |
Embodiment 5
400 liters of solution of preparation 25%Lupasol SC-86X (BASF), 1.5%Repearl MF (MitsubishiChemical company) and 0.1%WetAid NRW (Noveon) are put into this solution and are arranged in stretch tight the body lotion that pads on the frame of Montfort.Make that 6 sections (1-6) is dry, 100% polyester textile of open width by this solution, pads average pick up to obtain 106% by the compression roller that is set in 55psi with 23.5 yards/minute speed then.Then, make this fabric by being set at 320 baking oven; Fabric stops 14 seconds time under this temperature.Test this finished product fabric and absorb the ability that butyric acid is distinguished the flavor of, wash each arrangement type cloth specimen 20 times according to AATCC method 124-96 then, and test once more.Also test identical 6 sections of untreated cloth specimens in a like fashion as a comparison.Outcome record is in table 4.
Carry out following test: the butyric acid of 1 dilution is placed on the cloth specimen,, judges the group membership then and can hear this cloth specimen through after a while it being absorbed in the fabric.If any judge does not detect stink, then a denseer butyric acid solution is placed on this fabric, and estimates it once more.Repeat this process and can both smell the butyric acid flavor until all judges.Each judge writes down the concentration (ppm of unit) that he can detect the butyric acid of stink; This concentration is called the stink score value.The stink score value of average then each cloth specimen.
Table 4
Parameter stink score value mean value
Style is handled (being/deny) 0HL 20HL
1 is 1,000 600
1 denys 133 167
2 is 667 667
2 denys 83 117
3 is 867 667
3 denys 117 117
4 is 1,000 733
4 denys 67 167
5 is 1,000 533
5 denys 200 267
6 is 1,000 1000
6 denys 67 467
Claims (18)
1. the finishing agent that is used for fibre substrate comprises amine-containing polymer, crosslinking agent and volatile solvent with reactive group, wherein the anti-cleaning process of this finishing agent.
2. according to the finishing agent of claim 1, this finishing agent provides antimicrobial properties for fibre substrate.
3. according to the finishing agent of claim 1, this finishing agent is given the ability that undesirable body odor was eliminated or significantly reduced to fibre substrate.
4. according to the finishing agent of claim 3, wherein this ability can resupply.
5. fibre substrate, thus be included in the crosslinked resin-coated amine-containing polymer that forms anti-cleaning process on the fiber surface of this fibre substrate.
6. according to the fibre substrate of claim 5, this matrix has lasting antimicrobial properties.
7. according to the fibre substrate of claim 5, this matrix has lasting elimination or significantly reduces the ability of undesirable body odor.
8. according to the fibre substrate of claim 7, wherein this ability can resupply.
9. according to any one fibre substrate among the claim 5-8, this matrix is the synthetic fiber that also contain at least a extra finishing agent, and wherein extra finishing agent is anti-cleaning process.
10. according to the fibre substrate of claim 9, wherein extra finishing agent is a chemically-reactive dyes.
11. one kind for fibre substrate provides the method for antimicrobial properties, this method comprises:
Fibre substrate is exposed to comprises in the treatment compositions of amine-containing polymer, crosslinking agent and volatile solvent with reactive group; With
Solidify this fibre substrate;
Thereby make fibre substrate have lasting antimicrobial properties.
12. one kind for fibre substrate provides the method for eliminating or significantly reducing the ability of undesirable body odor, this method comprises:
Fibre substrate is exposed to comprises in the treatment compositions of amine-containing polymer, crosslinking agent and volatile solvent with reactive group; With
Solidify this fibre substrate;
Thereby make fibre substrate after the processing have lasting elimination or significantly reduce the ability of undesirable body odor.
13. according to the method for claim 12, thus this method also comprise the fibre substrate that makes after the processing be exposed to the pH value be 10 or the higher aqueous solution in resupply the step of fibre substrate odor absorption ability.
14. handle synthetic fiber matrix so that the method for durable finishing agent to be provided for one kind on this synthetic fiber matrix, this method comprises:
Fibre substrate is exposed to comprises in first finishing agent of amine-containing polymer, crosslinking agent and volatile solvent, so that treated fibre substrate has reactive group on its surface with reactive group;
Fibre substrate after the cured; With
Treated fibre substrate is exposed to comprise can with second finishing agent of the group of reaction-ity group reaction on the treated fibre substrate in;
Thereby producing wherein, second finishing agent is the synthetic fiber matrix of anti-cleaning process.
15., synthetic fibre substrate is exposed in first and second finishing agents simultaneously according to the method for claim 14.
16. according to the method for claim 14, wherein in being exposed to first finishing agent after, and before or after curing schedule, synthetic fiber matrix is exposed in second finishing agent.
17. according to any one method among the claim 14-16, wherein second finishing agent is a chemically-reactive dyes.
18., wherein before placing volatile solvent, the amine-containing polymer part is reacted with crosslinking agent according to any one method among the claim 11-17.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29755801P | 2001-06-11 | 2001-06-11 | |
| US60/297,558 | 2001-06-11 |
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| Publication Number | Publication Date |
|---|---|
| CN1514898A true CN1514898A (en) | 2004-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028116941A Pending CN1514898A (en) | 2001-06-11 | 2002-06-10 | Modification of fabric fibers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1404918A1 (en) |
| JP (1) | JP2004530062A (en) |
| CN (1) | CN1514898A (en) |
| WO (1) | WO2002101140A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113229A (en) * | 2015-09-15 | 2015-12-02 | 苏州顺唐化纤有限公司 | Softener for wear-resistant chemical fiber fabric and preparation method thereof |
| CN112918052A (en) * | 2021-01-28 | 2021-06-08 | 江苏厚生新能源科技有限公司 | Ultraviolet radiation-proof polyethylene fabric and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0225292D0 (en) * | 2002-10-30 | 2002-12-11 | Unilever Plc | Fabric care composition |
| WO2009045384A1 (en) | 2007-10-01 | 2009-04-09 | Nano-Tex, Inc. | Modification of cellulosic substrates to control body odor |
| EP4151797A1 (en) * | 2021-09-16 | 2023-03-22 | Livinguard AG | Antimicrobial textiles with adhered polycationic polymers and subjected to an acid treatment |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1455905A (en) * | 1964-05-28 | 1966-10-21 | New methods for the treatment of fibrous materials as well as products obtained | |
| US3885069A (en) * | 1972-08-11 | 1975-05-20 | Us Agriculture | Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine |
| PH11540A (en) * | 1975-05-30 | 1978-03-10 | Procter & Gamble | Nether garment for and method of controlling crotch odors |
| US4778813A (en) * | 1981-07-07 | 1988-10-18 | Buckman Laboratories International, Inc. | Polymeric quaternary ammonium compounds, their preparation and use |
| DE3329029A1 (en) * | 1983-08-11 | 1985-02-28 | Cassella Ag, 6000 Frankfurt | METHOD FOR PRODUCING COLORINGS WITH REACTIVE DYES |
| DE3709766A1 (en) * | 1987-03-25 | 1988-10-06 | Hoechst Ag | METHOD FOR ALKALI-FREE DYEING WITH REACTIVE DYES |
| DE4325783A1 (en) * | 1993-07-31 | 1995-02-02 | Hoechst Ag | Process for modifying and dyeing modified fiber materials |
-
2002
- 2002-06-10 JP JP2003503881A patent/JP2004530062A/en active Pending
- 2002-06-10 EP EP02756147A patent/EP1404918A1/en not_active Withdrawn
- 2002-06-10 CN CNA028116941A patent/CN1514898A/en active Pending
- 2002-06-10 WO PCT/US2002/018276 patent/WO2002101140A1/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113229A (en) * | 2015-09-15 | 2015-12-02 | 苏州顺唐化纤有限公司 | Softener for wear-resistant chemical fiber fabric and preparation method thereof |
| CN112918052A (en) * | 2021-01-28 | 2021-06-08 | 江苏厚生新能源科技有限公司 | Ultraviolet radiation-proof polyethylene fabric and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1404918A1 (en) | 2004-04-07 |
| WO2002101140A1 (en) | 2002-12-19 |
| JP2004530062A (en) | 2004-09-30 |
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