CN101023213A - Dressings which can be applied several times to textile fibres and textile fabrics - Google Patents
Dressings which can be applied several times to textile fibres and textile fabrics Download PDFInfo
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- CN101023213A CN101023213A CN 200580031279 CN200580031279A CN101023213A CN 101023213 A CN101023213 A CN 101023213A CN 200580031279 CN200580031279 CN 200580031279 CN 200580031279 A CN200580031279 A CN 200580031279A CN 101023213 A CN101023213 A CN 101023213A
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Abstract
The invention relates to a finishing agent, a finishing layer, finished textile fibre and woven textile, and a method used for finishing textile fibre and woven textile. Textile produced by using the invention can receive active material or active ingredients a plurality of times, and the active material or the active ingredients can be released to an ambient medium non-directionally according to the application function of the textile, or are released to a directly adjacent layer directionally locally led by matter flow. The finishing layer is characterized in the swellability and the capability of receiving active material of the finishing layer. A polymer layer is formed into a nanometer pocket which can receive one or a plurality of guest molecules during swelling. When processed clothing is worn, the active material is released and desorbed through temperature, water, friction and moving. Contrary to the known cyclodextrin based smart biologic textile, the invention can apply active material basically in a wider range on the surface of the textile a plurality of times. The active material can be released out when filled textile is worn, and can be absorbed by the skin of wearers through epiderm or percutaneously. In addition, the active material acts on target locations as required.
Description
The present invention relates to put in order the finishing agent that recharges (reloadable finish) on preparation (finish formulation) and textile fabric and the fabric, and the method that on textile fabric and fabric, applies such functional layer (functional layer).Similarly, the invention still further relates to based on the inventive method finishing agent textile fabric that handled or that obtain and fabric that can load repeatedly.
The market of coated fabric or the textiles put in order may be present fastest-rising market in the weaving department.To functional increasingly stringent that requires of coated fabric or the textiles put in order, and simultaneously severeer environment and consumer protection rules limit the scope of available chemicals and increase.Therefore, require collator (finisher) to use the limited raw material of range of choice to generate new product with function new and/or that strengthen.Document and practice have been described multiple influence and have been improved the coating that textile fabric prevented dust, refused water and/or refuses the surface property of oil, anti-UV, wear-resistant and/or resistance to chemical attack.In all these functions, the wearer of Special attention will be given to protection textiles makes it avoid some ectocine,, makes the health of some material away from wearer that is.
Term " intelligent textile " is present term in use, contained textiles known, that wear next to the skin, that have coating/finishing agent, it makes it possible to provide the clothes that contains treatment or cosmetic activity composition, when wearing this clothes, described treatment or cosmetic activity composition give to the skin of wearer or discharge from finishing agent.There is the scope of the active component of economic implications to comprise and imagines the material that obtains, comprise nicotine that cortisone from treatment neurodermatitis patient's ointment and ES (weaning smoker) the take anti wrinkling agent in the face cream.Existing people's suggestion provides anodyne, hormone, vitamin or preventing coating protection by such intelligence biological finishing agent continuously to skin.Also known antibacterium material can be used in the textiles, for example in underwear, socks, sweat shirt or the shoes, to prevent to produce unpleasant stink with perspiration.
Below except as otherwise noted, active component and active material are considered as medicine and health (wellness) material.The medicine rules with the former be defined as be applied to human body or animal body or in human body or animal body, use in order to treatment, alleviate, prevention or detect disease, pain, actual bodily harm or the material of disease symptoms and the composition of material.Healthy material is the holistic health sensation that is used to improve whole body ﹠ minds aspect of life, and makes spirit, health and mood and the material of coordination naturally.Healthy material also can be regarded as cosmetics hereinafter.Be included in based on " natural drug " in the medicine of above-mentioned classification and several active medicinal matters in the conventional medicament and application separately thereof and be summarized as follows:
Motion sickness: scopolamine, cinnarizine, meclizine;
Smoking cessation: nicotine;
Vein problem: heparin;
Hay fever: antihistaminic comprises cetirizine;
Muscle/arthralgia: diclofenac; And
Angina pectoris: glycerol trintrate.
The method that two kinds of different manufacturing intelligence finishing agents are arranged in textile finishing substantially.A kind of method is the cage shape molecule (cage molecule) that can load, for example cyclodextrin or dendritic (dendrimer) are coated on the surface to be applied, and another kind of method is that the polymer adhesive system (for example polyacrylate or polymethane) of will mix with each active component is coated on the textile substrates.Layer with cage shape molecular functionization can load repeatedly, this forms by the pre-mixture of polymer adhesive and active material with coated substance wherein and in the process of textile finishing as finishing agent apply layer different.
Two kinds of manufacture methods enumerating all are attended by the main shortcoming relevant with target application, particularly with the functional relevant shortcoming of finishing agent layer to be made.
With the range of application of the layer of cage shape molecule manufacturing be subjected to a great extent molecular dimension and geometry and with the restriction of the affinity of waiting to combine material, therefore only can be limited in the very narrow scope.For example, cyclodextrin is by 6 to 8 compound sugar that hollow-core construction is formed, had to glucose unit, and its outside has polarity OH base and inside has hydrophobicity.Therefore, only can be in conjunction with little lipophilic active substance, thus the application and the versatility of the finishing agent that contains cyclodextrin caused big restriction.As a result, the common cage shape molecule of carrying active material is mixed with dressing liquid, and be coated on the fabric by the textile finishing machine.Consider that the fabric of this arrangement obtains functional and the application of drafting in advance only can be made very limited amount to reduce marketing risk.This makes product very expensive, and the scope of product is also narrower.The layer made from " cage shape molecule " is relevant with respect to the ability of recharging after above-mentioned clothes washs with the advantage of the layer of polymer adhesive system manufacturing and they, and described ability of recharging depends in part on employed finishing agent.
The ability that the coating process of the polymer adhesive system of directly mixing with active material does not provide this to recharge.In this case, determine functional chemicals or active component in the arrangement process, to be coated on the textiles, thermal fixation in most of the cases takes place then.Most of objective function is lost in this fixation process.Wherein, active component generation thermal decomposition, or by change with fixing apparatus reaction, bonding or decompose, perhaps they evaporate with the heat medium air of discharge (for example with) and dissipate.Remain on the fabric the residual activity material only in various clothings are between limited operating period decision it is functional because the healthy layer of making by this method is not washable, and can not recharge.The result of above-mentioned shortcoming is very limited by the market of the fabric of this methodological functionization, and sells the risk height of this textile finishing machine.
The object of the present invention is to provide the arrangement preparation, the finishing agent that can recharge, the textile fabric of putting in order and the fabric that have overcome the inherent defect of existing product and method on the weaving market and the method for finishing textile fibre and fabric.
This purpose is used new arrangement preparation, new method for sorting, new finishing agent and textile fabric and the fabric realization of handling with new finishing agent.Special select chemicals---some of them are uncommon for the application in the textile industry, make it possible to obtain following effect, wherein:
I) new finishing agent can repeatedly load with multiple material, for example, uses the back or washs the back filling at corresponding clothes long-time, and make two kinds of controlled functional being attached in a kind of textile fabric according to the present invention's arrangement of independence become possibility;
Ii) on textile fabric, realized functional surface (object/host system), this can absorb it according to the application of expection and be mainly lipophile and be dominant the active material of (lipophilic-dominated) as guest species, and again with its non-directional be discharged in the surrounding medium, perhaps (locally-directed) material stream by local guiding directionally is discharged in the layer of direct neighbor.
In order to realize finishing agent of the present invention, the existing method and the new method of textile finishing all can be used, and the UV that described method for example is coated to the arrangement preparation on the textiles solidifies.
Finishing agent of the present invention can be designed to and as the active component releasing layer, or alleged " drug delivery system ", and/or as the harmful components absorbed layer.
An essential characteristic of the present invention is that finishing agent or the finishing agent layer that will follow host/object principle are coated on textile fabric or the fabric, and the host system with the wideest as far as possible range of application is provided, and this host system can reach interim filling repeatedly with various active composition or guest molecule.Host layer by the coating of textile finishing machine is the carrier of guest molecule, and this host layer can for example be applied by user oneself.Therefore, user's (for example, promptly wearing manufacturer, chemicals cleaner (chemical cleaner) or the wearer of type (ready-to-wear) clothing) can oneself determine each fabric or garment baffle usually.This becomes possibility by using following material: the crosslinkable polymer adhesive that combines with crosslinkable interval material (spacer substance), surfactant (emulsifying agent, dispersant or its mixture), common multifunctional crosslinking agent and any catalyst.After will being anchored on fiber or the fabric face by the finishing agent layer that above-mentioned chemicals forms, this finishing agent layer forms accepts the necessary host system of active material.
The swelling ability of the finishing agent that is generated is important for understanding the present invention.Use the polymer compound of preferred oleophylic modification and crosslinkable " feeler (tentacle) " or spacer molecule to generate than by polarity-protic and/or the stronger polymeric layer of the accessible swelling ability of polarity-proton inertia material.When this polymeric layer swelling, in the finishing agent layer, form at random nanometer pocket (nano-pocket) (relevant and depend on the space of employed interval dose (spacer) expand) with molecular dimension.These nanometer pockets can be accepted one or more guest molecules, because their space structure and polarity can be according to waiting that the molecular dimension of accepting object adjusts.Nanometer pocket preferred maximum dimension is 500 nanometers.When the fabric of this method arrangement is passed through in dress, one or more guest species, promptly the active material of being accepted discharges also desorb once more by means of body temperature, moisture, friction and mobile quilt.Active material is according to its kind, and skin that can the person of being worn absorbs through epidermis or through skin, and applies required effect in desired location.
Use crosslinkable surfactant to make the finishing agent component produce the self-organizing space, that thermodynamics is induced (self-organization) effect simultaneously, this effect has determined the affinity of finishing agent layer to the leading active material of oleophylic on the one hand, and has determined the physiology behavior of finishing agent layer to human body skin on the other hand.
In case after generating the finishing agent layer, the nanometer pocket promptly is present in the finishing agent layer of swelling not with the alleged form of caving in (collapsedform).Nanometer pocket potential after the finishing agent set is contacting postforming with following material: moisture and treat absorbing material or compounding substances to be absorbed, these materials can be the aqueous emulsion of active material to be absorbed or the mixture of active material in preferred embodiments.Form the amount ratio and the selection thereof of the chemicals of polymeric layer, represented by the finishing agent layer and accepted and separate out the controlled parameter of active material.
Except the nanometer pocket, finishing agent layer of the present invention can have micron hole and/or mesopore as additional structure.For this reason, can when make the arrangement preparation, for example, sneak into and to separate out CO
2Or N
2Material, and/or add non-reacted volatile solvent.In drying and/or fixation process, the gas that discharges or the non-reactive solvent of effusion produce micron order or intermediate capillarity (diafiltration bunch (percolation cluster)) in the finishing agent layer, wherein the size range of micron hole and mesopore is 1 to 25 μ m.Active surface appreciable impact absorption of active agents behavior or the desorb behavior to be coated that enlarges greatly in this way.
The dynamic formation that another essential characteristic of functional finish by this method manufacturing is to load the ability of finishing agent repeatedly and active material is had specific nanometer pocket.This function is at first determined by the type and the concentration of the interval material that exists in the finishing agent layer.
Another of finishing agent of the present invention is functional to be obtained by following dual mode: cage shape molecule is sneaked in the arrangement preparation, or cage shape molecule is coated to separately possessed the of the present invention of polymeric layer that contains the nanometer pocket and load on the textiles.Except known cyclodextrin, must mention beta glucan and zeolite especially.Beta glucan is a kind of polymer of polysaccharide structures, and it forms as waste product in the preparation process of yeast.
After fat in the beta-glucan products and protein removed, should promptly can be used as cage shape molecule.Zeolite is the silicate of water-bearing structure, and its lattice structure can be held multiple CATION on the one hand, and the gap between the zeolite granular can hold guest molecule on the other hand.
Two kinds of host system (the dynamic formation of nanometer pocket and cage shape molecule) there are differences aspect the mechanism of accepting the different activities material, the former forms the nanometer pocket by means of the ratio of component of finishing agent layer, and the latter is by the interaction between the functional and structural of employed cage shape molecule and they and the finishing agent component.For example, the advantage electric charge (chargedominance) (anion, nonionic, CATION) of cage shape molecule influences the ability that it absorbs active material with employed finishing agent component.These parameters have been determined absorption or the performance of desorb order of priority, for example polarity, compatibility, geometry and the space structure etc. of decision guest molecule.
Except correct selection finishing agent chemicals and mixing ratio thereof, the drying and the set condition of chemicals that is suitable for containing the host is also extremely important for form the nanometer pocket in host system.The chemicals that forms the host at first mixes to generate coating liquid (dressing liquor) or arrangement preparation.For this reason, a kind of main component provides with the form of at least a polymer compound, and it is preferably by (C crosslinkable, fatty modification
2To C
18), the acryloyl group polymer of water and milkization, epoxy polymer or urethane ester polymer form.Add the chemicals as interval dose then, it contains the molecule " feeler " with at least one end reaction base on the one hand, and execution interval function on the other hand.The chemical constitution of molecule " feeler " or interval dose comprises polyether chain, the polyether chain that for example has terminal hydroxyl, amino, carbonyl, carboxyl, acid amides, isocyanates, N-hydroxyl methyl alcohol or methoxyl group-N-methyl alcohol functional group (alpha-aminoalkyl product), described polyether chain preference such as polyoxyethylene, polyoxypropylene, block polymer and/or C
2To C
18Chain.
Preferably at least a multi-functional artificial resin compound is added in the coating liquid to serve as crosslinking agent (alpha-aminoalkyl product as another kind of component, the for example ethylene urea of methoxylation or melamine compound), this compound plays an important role in the configuration aspects of the washability, swelling ability and the nanometer pocket that help to determine the finishing agent layer.
Catalyst is with the material of doing the cross-linking reaction between the composition is risen catalytic action, for example magnesium chloride, single carbonic acid and many carbonic acid or go out the ester of compound as acid out.
For compatibility and the physiology behavior of controlling the finishing agent layer, in coating liquid, add surfactant or surfactant mixtures.Surfactant is generally anion and nonionic, for example the anhydrosorbitol derivative of glycerine citrate, glycerol monolaurate, fatty modification (for example being selected from the emulsifying agent of span and poly-span series), cetaryl glucoside, poly-olein, poly-tristerin and siloxanes polyglycol ether and/or siloxanes polyglucoside, its HLB value (hydrophilic-lipophilic balance (HLB)) is in 3 to 15 scope.
For specific purposes, for example when needing the highest big loadings and high rate of release, can choose use has expansion to the finishing agent layer bubbing (CO wantonly
2And N
2As foamed gas) non-reactive material.This purpose is closely related with the absorption and desorption of the material that gives out stink.The required micron hole/mesopore percolation structures of finishing agent layer obtains by adding following material: separate out CO
2And N
2The organic substance of foamed gas (for example acetoacetate, 2,2 '-azodiisobutyronitrile, 2,2 '-azo two-(2-methylpropane)) is separated out CO
2Inorganic substances (for example sodium bicarbonate is with the catalyst of separating out acid) and boiling point be 60 to 200 ℃, the preferred 120 ℃ non-reacted swelling solvent of polarity (for example ethyl acetate, ethylene glycol-methyl ether acetate, diethylene glycol dimethyl ether).
In the second road processing step, use the coating liquid that the standard industry coating technology will contain host's chemicals to be coated on the textiles, described standard industry coating technology, for example, pad dyeing, coating or spraying.In order to improve the scourability of host system, especially for composite fibre materials, can apply the adhesive phase that contains reactive group in advance, claim prime coat again.These prime coats are known in for example WO 01/75216.The coating of prime coat is a processing step that carries out prior to the host layer coating.Expection according to the fabric that has host layer is used, and can use general application system, and for example batch (-type) pads (stop padding), plays the not host layer of same-action, for example host layer of compatibility difference (lipophile is higher or lower) to apply two kinds.
The 3rd road processing step wanted of overstating for producing the nanometer bag structure comprises the dry fabric that has flooded (residual water content at the most 30%), and making the set of finishing agent layer then, this can be undertaken by using dry method set technique (at 120 to 180 ℃) and wet method set technique (at 15 to 40 ℃).The fabric put in order uses industrial equipment for example stenter or airflow dryer under 50 to 150 ℃ temperature dry 30 to 180 seconds.When set finishing agent layer,, preferably use thermal reaction apparatus and/or UV radioreaction device according to employed polymer/cross-linking system.Thermal fixation takes place under 120 to 200 ℃, preferred 140 to 160 ℃ temperature, and the reaction time is 1 to 5 minute.When using the UV cured polymer, according to the type of polymer with to the radiant power of reaction collective (aggregate), 0.5 to 60 second, preferred 1 to 3 second reaction time are necessary.Use a major advantage of UV cured polymer to be and at low temperatures washable layer to be anchored on the textile substrates.As a result, when being applied as layer chemicals, functional layer can be loaded active material, even the pyrolysis and/or the volatilization of the normal guest species that takes place originally occur.
Following examples have illustrated the example of selecting from the manufacture method of the finishing agent layer of the preferred finishing agent preparation of the present invention, formation nanometer pocket, and their efficient with regard to desired function has been described.
Embodiment 1: the finishing agent layer that is used to produce the diafiltration bunch of nanostructured
With every weight per square meter is 210g/m
2, cleaning and the cotton blended fabrics (75%Co, 25%PES) bleached are with the dressing liquid dipping in advance, the component of this dressing liquid forms the nanometer pocket in the dry run of fabric, i.e. the diafiltration of nanostructured bunch.The fabric coating that contains the nanometer pocket both can be used as the drug delivery system that can recharge, and also can be used as simple absorbed layer, for example absorbed the absorbed layer of the material that gives out stink.
The arrangement preparation that is coated to fabric face is 11% with respect to the mass fraction of dry fabric weight.After fabric usefulness being contained the dressing liquid dipping of finishing agent component, make it following dry 120 seconds at 120 ℃.
The arrangement preparation contains following component:
The arrangement preparation of table 1: embodiment 1
| The dressing liquid component | Concentration |
| Water | ?786.5 |
| ?Dicrylan?AS | ?150g/l |
| ?Glucan?P20 | ?45g/l |
| ?Lyofix?CHN | ?12.5g/l |
| Magnesium chloride | ?6g/l |
Dicrylan AS is the water-borne dispersions of 40% acrylate sold of ERBA, when it combines with other formulation components generation soft, the Hypoallergenic coating.
Glucan P20 is crosslinkable propenoxylated glucose, and it serves as the interval dose that forms the nanometer pocket, and described nanometer pocket after by host system being produces the activating agent (object) that applies.
Lyofix CHN is a kind of artificial resin (hexamethylol-melamine resin of part etherificate), and it makes the finishing agent component crosslinked, and with other formulation components and catalyst (MgCl
2) in conjunction with the time produce washable permanent fabric coating.
Coating was 150 ℃ of following sets 3 minutes.
When immersion contained in the aqueous emulsion of one or more active materials, the coating by the said method manufacturing can form the diafiltration bunch of the nanostructured that is filled with (one or more) active material.
Embodiment 2: according to the dynamic nanometer pocket of adjusting of guest species
To by 30% cotton and 70% polyamide is formed, every weight per square meter is to put preparation in order by dip coating on the BLENDED FABRIC of boiling and bleaching of 165g, described arrangement preparation is called coating compound below again, and its representative will be made the host system of the guest species (being active material) of back coating at fabric.The finishing agent that anchors at fiber surface is 8% with respect to the mass fraction of the dry weight of untreated fabric.After BLENDED FABRIC usefulness being contained the dressing liquid dipping of coating compound, make it descend dry 60 seconds, and make the finishing agent layer that contains the nanometer pocket that in dry run, forms 150 ℃ of following sets 180 seconds at 130 ℃.Maceration extract contains following component:
The arrangement preparation of table 2: embodiment 2
| The dressing liquid component | Concentration |
| Water | 799.4g/l |
| Subitol?ES | 3g/l |
| Dicrylan?AS | 104g/l |
| Ethyl-hydroxy ethyl cellulose | 7g/l |
| Pluriol?P?600 | 30g/l |
| The lauryl anhydrosorbitol | 10.6g/l |
| Lyofix?MLF | 36g/l |
| Magnesium chloride | 8g/l |
| Citric acid | 2g/l |
Subitol ES (Bezema AG) is a kind of based on the crosslinked of anion surfactant and block auxiliary agent.
DICRYLAN AS be a kind of aqueous coating that is used for textile fiber material can chemistry/heat cross-linking the nonionic polyacrylate dispersion.
Pluriol P 600 (BASF) is the polypropylene glycol of a kind of average molar mass for about 600g/ml, and it is used to suppress foam, gives solubility, changes polarity and denseness.
LYOFIX MLF (ERBA) is the nonionic hexamethylol melamine resin of the lower part etherificate of a kind of content of formaldehyde, and it is as the DIMENSIONAL STABILITY finishing agent of the mixture of cellulose and cellulose and synthetic fiber.With based on the conventional crosslinking agent of melamine relatively, it has lower content of formaldehyde and extraordinary buffering effect, and reaches good washing and flatiron/shrink value (shrinkage value), good basic effect and extraordinary performance.
Be exposed to and contain 20% isooctanol in the aqueous emulsion of---lipophile healthy material model substance (modelsubstance)---after 12 hours, the octanol of the finishing agent layer that is produced by this dressing liquid absorbs and is up to 16% of layer quality.With after 50% water/ethanolic solution filling and extracting three times, 16% octanol that still can reappear initial mensuration absorbs with the finishing agent layer.
This test shows, even final user, also available lipophilicity substance loads the finishing agent layer repeatedly, and he can freely select the functional to reflect its demand of finishing agent layer in this case.
Embodiment 3: the functionalization finishing agent with nanometer pocket that is used for nerve skin class patient
The knitted fabric that is 230g to weight per square meter that be made up of polyester and lycra, every before dyeing carries out Chemical cleaning to remove fiber preparation, dyes then.Use first application needle envers one side (batch (-type) pads) to apply outer field application system then coating compound is coated on the also dry knitted fabric that dyes, wherein coating compound is as host system, can absorb lipophilic active substance, for example phenol carbonic acid, farnesol or the gamma-Linolenic acid (evening primrose oil) of the root extract of wild marjoram or Arctium as object.The functional of finishing agent layer only determined by selecting active component to be applied by the people who wears clothes.The root extract of wild marjoram and Arctium has antifungal and bacteriostasis, and farnesol only has bacteriostasis, and evening primrose oil can be alleviated the skin itching that is caused by neurodermatitis.The coating that contains the nanometer pocket prepares by the following method: with following dressing liquid dipping knitted fabric, make it then 120 ℃ of dryings 80 seconds, and 160 ℃ of sets 180 seconds.The quality of coated finishing agent layer is 12% of a knitted fabric dry weight.Below the component of finishing agent layer and concentration thereof are listed in.
The arrangement preparation of table 3: embodiment 3
| The dressing liquid component | Concentration |
| Water | ?717.5g/l |
| ?Invadin?PBN | ?2.5g/l |
| ?Perapret?HVN | ?120g/l |
| Ethyl-hydroxy ethyl cellulose | ?10g/l |
| ?Pluronic?PE?3100 | ?39g/l |
| ?Drapal?GE?202 | ?42g/l |
| ?Lyofix?MLF | ?54g/l |
| Magnesium chloride | ?15g/l |
Invadin PBN (ERBA) is a kind of surface-activity preparation of being made up of the fatty alcohol and the aliphatic ether alcohol of ethoxylation, and it is as the special crosslinking agent of refusing water and oil-refusing finishing agent.
Perapret HVN is a kind of anionic polyacrylate dispersion of the thermally cross-linkable that is provided by BASF, is used to put in order tatting product and the knitwear of being made up of the mixture of cellulose and cellulose and synthetic fiber.
Pluronic PE 3100 is a kind of by making the product of the BASF that expoxy propane and oxirane copolymerization make, and it is as low foaming surfactant.
Drapal GE 202 (Akzo Chemie) is a kind of branching carbonic acid copolymer that contains hydrophobic alkyl and hydrophily ether and have the partial esterification of emulsification property.
LYOFIX MLF (ERBA) is the nonionic hexamethylol melamine resin of the lower part etherificate of a kind of content of formaldehyde, and it is as the DIMENSIONAL STABILITY finishing agent of the mixture of cellulose and cellulose and synthetic fiber.With based on the conventional crosslinking agent of melamine relatively, it has lower content of formaldehyde and extraordinary buffering effect, and reaches good washing and flatiron/shrink value, good basic effect and extraordinary performance.
For the finishing agent layer made from above-mentioned preparation,, make its filling wild marjoram or the root extract of Arctium and aqueous emulsion of farnesol by one side of the knitted fabric that contains coating being sprayed from a side.After exposing 12 hours, softly wash a slice knitted fabric and make its drying.Then a washed knitted fabric that contains active component is placed on the agar gel that fungus attack crosses with a untreated knitted fabric, and was placed in 30 ℃ the temperature and humidity condition regulating box three days.
After three days, overgrow with the mould culture in a large number on the untreated knitted fabric piece, the knitted fabric piece that contains finishing agent and loaded Arctium root extract and the farnesol then desorb by active material has stoped fungus growth on the agar layer that this sample covers fully.
This embodiment shows that the desorb of the filling of host layer and guest species applies antifungal and bacteriostasis according to the application of expection in this embodiment.
Embodiment 4: have the finishing agent of inhaling smelly (odor-absorbing) effect
Dye and drying after will washing in advance by 30% BLENDED FABRIC cotton and that 70% polyester is formed.Fabric face carries out functionalization by applying the finishing agent layer with following composition:
The arrangement preparation of table 4: embodiment 4
| The dressing liquid component | Concentration |
| Water | ?747g/l |
| Subitol?LS-N | ?3g/l |
| Dicrylan?AS | ?120g/l |
| Methocell?311 | ?12g/l |
| Polypropylene glycol | ?30g/l |
| The siloxanes polyglycol ether | ?8g/l |
| Knittex?FPC | ?55g/l |
| Knittex catalyst MOF | ?10g/l |
| Azodiisobutyronitrile | ?15g/l |
Subitol LS-N is a kind of low foaming anionic crosslinking agent based on synergy surfactant (synergisticsurfactant) mixture, and it is sold by the CHT company of T ü bingen.
Methocell 311 is a kind of cellulose ethers of being produced by DOW Europe S.A..
Knittex FPC (ERBA) is a kind of nonionic reactant crosslinking agent of the glyoxal crosslinking agent based on modification, be used for cellulosics and composition thereof low formaldehyde, anti-boil wash, noniron finish.
Knittex catalyst MOF (ERBA) is a kind of liquid acid donor (aciddonor) based on magnesium salts, and it is preferred for the high finish agent is coated on the cellulosics.
Azodiisobutyronitrile is as separating out N
2Swelling agent.
Contained chemicals is guaranteed the formation of nanometer bag structure and the polarity that is suitable for absorbing oleophilic substance on the one hand in the dressing liquid, guarantee on the other hand adsorbent adsorb fast with desorb required the layer porous.Be the manufacturing function layer, with fabric with above-mentioned dressing liquid (liquid adsorption 80%) dipping and 110 ℃ of dryings 180 seconds.Functional layer is passed through with the stenter cohesion subsequently 150 ℃ of following sets 3 minutes.For preventing that adsorbed material is exposed to bacteria attack---this originally often takes place, and is filled with a spot of farnesol (finishing agent layer weight about 2%) in the finishing agent layer.
After the farnesol filling, embodiment 4 described finishing agents are used to adsorb the material that gives out dense smell, for example the material that runs in restaurant or the kitchen, restaurant.After restaurant job personnel's Work Clothes used the finishing agent of embodiment 4, described Work Clothes or this type men and women coat no longer were subjected to the invasion of any smell, even also be like this after wearing three days.Even the odor-absorbing energy of described farnesol is also kept behind the clothes cyclic washing, wherein clothes or finishing agent layer must load with farnesol in each washing back.
Embodiment 5: the bi-component finishing agent with nanometer pocket and cage shape molecule
The knitted fabric of being made up of 100% polyamide is removed and is dyeed behind the fabric softening and dry.Subsequently in the first road processing step with the chemicals dipping knitted fabric that forms the nanometer pocket, and 120 ℃ of dryings 2 minutes.In the second road processing step, pad with the suspension that contains anionic glucan (cage shape molecule) by one-sided batch (-type) and to apply through the carboxylation modification, wherein cage shape molecule is filled with silver complex in advance.Then, carry out drying and make the chemical set of two kinds of host system (nanometer pocket and cage shape molecule), this two kinds of host system functional is because advantage electric charge difference (nanometer pocket host is a nonionic, and cage shape molecule host is an anionic) and difference.The quality that is coated to the finishing agent of the formation nanometer pocket on the knitted fabric accounts for 10%, and the quality that contains the finishing agent of glucan accounts for 1%, all with respect to the quality meter of unfinished knitted fabric.In the first road processing step, apply, residual moisture is that composition in 72% the coating liquid is as follows:
The first arrangement preparation of table 5: embodiment 5
| The dressing liquid component | Concentration |
| Water | ?780g/l |
| ?Subitol?ES | ?2.5g/l |
| ?Dicrylan?AS | ?140g/l |
| ?Bermocoll?E?230?FQ | ?5g/l |
| ?Pluronic?P?3500 | ?23g/l |
| ?Lyofix?MLF | ?30g/l |
| ?Drapal?GE?202 | ?10g/l |
| Magnesium chloride 6H2O | ?8g/l |
| Citric acid | ?1.5g/l |
BERMOCOLL E 230 FQ (Akzo Nobel) are a kind of water-soluble cellulose ethers (the ethyl hydroxy ethyl cellulose of low viscosity level) of nonionic, and it improves the denseness and the stability of water based product.
Pluronic P 3500 (BASF) is the block copolymer of polypropylene glycol and oxirane, and substantially as nonionic surface active agent.
In the second road processing step, pad the glucose suspension that is coated on the clothes filling side (bearing side) subsequently from a side by batch (-type) and form by following component:
The second arrangement preparation that contains glucan of table 6: embodiment 5
| The dressing liquid component | Concentration |
| Water | 964g/l |
| Beta glucan (anion-modified and be filled with silver complex) | 25g/l |
| Glutaraldehyde | 8g/l |
| Acetate 80% | 1g/l |
| Subitol?ES | 2g/l |
This finishing agent has reflected the multi-functional layer of the clothing that is used to wear next to the skin, and wherein wearer has drying, squamous or susceptible skin.Described finishing agent has the significant bactericidal action of the glucan cage shape molecule that snow cover fills out, and skin also is able to re-lubrication and humidification by the active component that loads in the nanometer pocket, produces bacteriostasis.For this reason, the functional layer that will contain the nanometer pocket is with the aqueous emulsion filling that contains Linseed oil, urea, gamma-Linolenic acid and farnesol 12 hours, and detects on the gel of simulating human skin and separate out effect a couple of days.The desorb after four days in the Franz diffusion cell of above-mentioned active material only can detect about 17% of the initial active material quality that exists in the nanometer bag structure.Positive according to expectation, remaining active material quality of 83% is present in the diffusion gel of simulating human skin.
Based on the above-mentioned multifunctionality of finishing agent layer, it is absolute ideal in the use in the clothing that wears next to the skin for the neurodermatitis patient.
Embodiment 6: other have the bi-component finishing agent of nanometer pocket and cage shape molecule
The knitted fabric of being made up of 100% polyamide dyes, cleans after cleaning in advance and carries out post processing with tannin.Gan Zao knitwear are at first put in order with the chemicals that forms the nanometer pocket, are similar to embodiment 5.In ensuing processing step, spray with the suspension of silver zeolite.Drying subsequently and cohesion are about to two kinds of host system (nanometer pocket and silver zeolite) and anchor on the knitted fabric.Selected coating amount and embodiment 5 described amounts are similar.After the chemicals that applies in the first road processing step was coated, its residual moisture was 75%.The dressing liquid that contains silver zeolite that sprays on the knitted fabric is made up of following component:
The arrangement preparation that contains silver zeolite of table 7: embodiment 6
| The dressing liquid component | Concentration |
| Water | 956.5g/l |
| Silver zeolite | 30g/l |
| The acryloyl group polymer | 12g/l |
| Subitol?ES | 1.5g/l |
The expection of mentioning among the functional embodiment of can be used for 5 of the finishing agent layer of being made up of two kinds of host system is used.Use the zeolite do not load or be filled with other materials (beyond the desilver) to make it possible to produce that other are functional.
In the situation of the finishing agent that uses heat cure and/or UV or blue light to solidify, prepolymer that the host system of accepting active component and active material (object or medicine) is solidified by heat cure and/or UV or blue light or monomer and at least aly have that the component and the surfactant of function are formed at interval.The host system that makes up by this method can be by containing the aqueous emulsion swelling of active component and active material, and can adsorb active component contained in the emulsion and active material and it is discharged once more.
Surfactant is monomer and/or the polymer that contains reactive group, and its HLB value preferably fluctuates between 8 and 12 between 3 and 16.Exemplary surfactants comprises sorbitan laurate or stearate, simple glyceride and diglyceride, has the ethoxylation and/or the propenoxylated C of 10 to 30 EO unit
8To C
20Compound or vinyl or allyl ether alcoxylates (alkoxylate), the reactive group that they and nucleophilic are dominated for example amino and hydroxy functional group formation addition or condensation product.
The interval material that helps to determine finishing agent layer swelling situation is generally the RG-RS-RG type.The reactive group that RG solidifies corresponding to UV or blue light or with the crosslinked functional group of such reactive group, and RS is corresponding to making the residue of material characterization, for example polyethers, polyester or vinylogue chain at interval:
[-CH
2-CH
2-O-]
n，
[-CH(CH
3)-CH
2-O-]
n，
[-CH
2-CO-O-(CH
2)
x-O-]
n，
[CH (CO-O-(CH
2)
x-CH
3)-CH
2-]
n, or
The chain length of determining material hydrophily at interval or hydrophobic residue RS is limited by n and x, and wherein n is preferably greater than 5 and less than 30, and x is preferably between 2 and 4.
The antibacterial finish agent that embodiment 7:UV solidifies
To form by cotton and polyester, every weight per square meter is the fabric of the 170g also drying that dyes after preliminary treatment (destarch and bleaching).With the coating ingredients dipping of fabric with healthy active component and formation " micron pocket ", its chemical set only just takes place after fabric solidifies drying by UV then.Use that UV solidifies, as to generate nanometer pocket finishing agent component to make it possible to when making the finishing agent layer, use healthy active material, and needn't worry the material damage that its chemical modification or heat cause.
The preparation that below has the finishing agent of bacteriostasis has illustrated this embodiment:
The antibacterial finish preparation of the UV-curable of table 8: embodiment 7
| The dressing liquid component | Concentration |
| Water | 77.7％ |
| Emulsoge?R109 | 1.5％ |
| Dicrylan?AS(40％) | 10％ |
| OTA?480 | 6％ |
| The methacrylic acid stearyl | 4％ |
| 2-hydroxy-2-methyl-1-phenyl-1-acetone | 0.3％ |
| Farnesol | 0.5％ |
Dressing liquid is coated on the fabric with ironer, and blockage effect (pinch-off effect) is 75%, and following dry 2 minutes at 110 ℃ with stenter.
After the finishing agent layer passes stenter, carry out UV at once and solidify.Being solidificated under the protective atmosphere of finishing agent layer continues 2.5 seconds in the UV passage.
Fabric with this method arrangement is characterised in that weak hydrophobicity and bacteriostasis.The clothing that this fabric is made is after washing, and available farnesol makes bacteriostasis regeneration.
Embodiment 8: finish coating UV-curable, that can recharge
With every weight per square meter is 180g/m
2, in advance the fabric of dyed polyamide of cleaning with Rewin RT (BEZEMA AG) solution impregnation of 5g/l to improve dyefastness.In second step, with the arrangement preparation dipping of tentering ironer preliminary treatment and dry fabric use emulsion form.The preparation and the composition of emulsion will be described below.
Emulsion is prepared by following component:
The arrangement preparation of the UV-curable of table 9: embodiment 8
| The dressing liquid component | Concentration (%w/w) |
| Water | 93.0 |
| Superonic?PE/F?108 | 1.40 |
| OTA?480 | 2.10 |
| UVR?6105 | 1.61 |
| Pluronic?PE?6200 | 1.05 |
| The ethyl hydroxy ethyl cellulose | 0.21 |
| Sorbitan monolaurate | 0.35 |
| 2-hydroxy-2-methyl-1-phenyl-1-acetone | 0.28 |
The propenoxylated trimethylolpropane triacrylate that OTA 480 sells for UCB.
Superonic PE/F 108 be Unicema the vinyl ethers alcoxylates (about 14,000g/mol).
The epoxy resin of UVR 6105 expression Dow.
Water and Superonic PE/F 108 are fully mixed.In this mixture, divide aliquot to add the mixture of OTA 480, UVR 6105, Pluronic PE 6200, ethyl hydroxy ethyl cellulose, sorbitan monolaurate and 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Subsequently, will be with tentering ironer (tentering frame foulard) with the fabric crossed with liquid infiltration with respect to 80% rate of application of textiles dry weight 120 ℃ of dryings 2 minutes, and after drying, pass the UV passage so that the set of finishing agent layer.Reaction time in the UV passage is at 5.5kW/m
2Particular radiation power under be 2.5 seconds.The UV passage preferably is full of protective gas, for example nitrogen, CO
2Or argon gas, so that in the radically curing process of acrylate, avoid any undesired oxidizing process on the one hand, and prevent the formation of ozone on the other hand.
The difference of the fabric finishing agent of Sheng Chaning is good host characteristics by this way, and the feature of these host characteristics is swelling ability that host layer is good and to the high-affinity of oleophilic substance.The layer of making in this way shows the ratio material absorption of the every gram host layer 23mg isooctanol model substance of the active material of improve looks (be used for the treatment of and/or).Another basic standard of host's performance is each clothing the recharging of host layer after washing.The ability that the finishing agent layer recharges still is 82% of former isooctanol absorbability after five washings.
Except with the functional relevant performance of the finishing agent layer of UV-curable, also must mention its cost-efficient manufacture method, because omitted the high temperature set effect of common generation.The finishing agent component of using UV to solidify makes it possible to use when making the finishing agent layer or add required active material, and needn't worry the material damage that its chemical modification or heat cause.
Claims (45)
1. arrangement preparation that is used on textile fabric and fabric making finishing agent, comprise a kind of crosslinkable polymer adhesive, a kind of surfactant and a kind of general multifunctional crosslinking agent, it is characterized in that said composition comprises crosslinkable interval material, and it is after the polymer adhesive with preferred oleophylic modification combines, and can produce that have can be by polymer finishing agent layer nanometer pocket, that can load active material repeatedly of polarity-protic and/or polarity-non-proton property material swelling.
2. the arrangement preparation of claim 1 is characterized in that polymer adhesive is selected from the C of the water and milkization of crosslinkable, fatty modification
2To C
18Acryloyl group polymer, epoxy polymer, vinyl acetate polymer, vinyl pyrrolidone polymer and block polymer thereof or urethane ester polymer.
3. claim 1 or 2 arrangement preparation, it is characterized in that polymer adhesive with respect to the dry matter content of finishing agent layer to be made with 40 to 80%, preferred 50 to 65% percentage exists.
4. one arrangement preparation in the claim 1 to 3 is characterized in that adding multi-functional artificial resin compound, preferred alpha-aminoalkyl product, and for example the ethylene urea of methylolation and/or methoxylation or melamine compound are as crosslinking agent.
5. one arrangement preparation in the claim 1 to 4, it is characterized in that crosslinking agent with respect to the dry matter content of finishing agent layer to be made with 5 to 40%, preferred 10 to 20% percentage exists.
6. one arrangement preparation in the claim 1 to 5 is characterized in that material is selected from interval: polyether chain, preferred polyoxyethylene, polyoxypropylene, block polymer and/or C
2To C
18Chain, described polyether chain preferably have terminal hydroxyl, amino, carbonyl, carboxyl, acid amides, isocyanates, N-hydroxyl methyl alcohol or methoxyl group-N-methyl alcohol functional group.
7. one arrangement preparation in the claim 1 to 6, it is characterized in that material at interval with respect to the dry matter content of finishing agent layer to be made with 5 to 40%, preferred 10 to 25% percentage exists.
8. one arrangement preparation in the claim 1 to 7 is characterized in that adding and is selected from following material as crosslinking catalyst: magnesium chloride, single carbonic acid and many carbonic acid or go out the ester of compound as acid out.
9. one arrangement preparation in the claim 1 to 8, it is characterized in that crosslinking catalyst with respect to the dry matter content of finishing agent layer to be made with 1 to 8%, preferred 2 to 4% percentage exists.
10. one arrangement preparation in the claim 1 to 9, it is characterized in that adding the HLB value in 3 to 15 scopes anion and nonionic as surfactant, wherein surfactant is selected from: the anhydrosorbitol derivative of glycerine citrate, glycerol monolaurate, fatty modification---be preferably selected from emulsifying agent, cetaryl glucoside, poly-olein, poly-tristerin and the siloxanes polyglycol ether and/or the siloxanes polyglucoside of span and poly-span series.
11. one arrangement preparation in the claim 1 to 10, it is characterized in that surfactant with respect to the dry matter content of finishing agent layer to be made with 2 to 25%, preferred 5 to 8% percentage exists.
12. one arrangement preparation in the claim 1 to 11 is characterized in that adding when making the arrangement ghe layer and can separate out CO
2And/or N
2And/or be to expand non-reacted material with the generation and the space of percolation structures in control finishing agent layer-fibre composites with swelling action.
13. the arrangement preparation of claim 12 is characterized in that separating out CO
2And/or N
2The material of foamed gas comprises and is selected from acetoacetate, 2,2 '-azodiisobutyronitrile and 2, the organic substance of 2 '-azo two-(2-methylpropane), thus and/or combine with the catalyst of separating out acid and to separate out CO
2Inorganic substances---sodium bicarbonate.
14. the arrangement preparation of claim 12 is characterized in that preferably adding boiling point and be 60 to 200 ℃, preferred 120 ℃ ethyl acetate, ethylene glycol-methyl ether acetate and/or diethylene glycol dimethyl ether are as the non-reacted swelling solvent of polarity.
15. one arrangement preparation in the claim 1 to 14, it is characterized in that the swelling material with respect to the dry matter content of finishing agent layer to be made with 1 to 15%, preferred 2 to 5% percentage exists.
16. one arrangement preparation in the claim 1 to 15 is characterized in that it comprises the cage shape molecule that is selected from cyclodextrin, dendritic and/or glucan.
17. one arrangement preparation in the claim 1 to 16, it is characterized in that cage shape molecule with respect to the dry matter content of finishing agent layer to be made with 1 to 20%, preferred 8 to 15% percentage exists.
18. one arrangement preparation in the aforementioned claim is characterized in that the photo-crosslinking in the visible-range of light in the UV scope of its available 100nm to 400nm or 400nm to 800nm.
19. the arrangement preparation of claim 18 is characterized in that prepolymer or monomer and at least a component and surfactant with interval function that it comprises that heat cure and/or UV or blue light are solidified.
20. be used for the finishing agent of textile fabric and fabric, it is characterized in that it uses in the aforementioned claim one arrangement preparation manufacturing, and can pass through polarity-protic and/or polarity-non-proton property material swelling, and it has the nanometer pocket that can load active material repeatedly under solvent swelling state.
21. the finishing agent of claim 20 is characterized in that the nanometer pocket shows as random distribution with regard to expanding in its space.
22. the finishing agent of claim 20, it is characterized in that the nanometer pocket-sized on be limited to 500nm.
23. the finishing agent of claim 20 is characterized in that it shows micron order or intermediate capillarity, wherein the size range of micron hole and mesopore is 1 to 25 μ m.
24. one finishing agent in the claim 20 to 23 is characterized in that it comprises the cage shape molecule that is selected from cyclodextrin, dendritic or glucan or its mixture.
25. one finishing agent in the claim 20 to 24 is characterized in that it comprises silver zeolite.
26. make one textile fabric and the method for the finishing agent on the fabric in the claim 20 to 25, it is characterized in that using at least a claim 1 to 19 one arrangement preparation.
27. the manufacturing textile fabric of claim 26 and the method for the finishing agent on the fabric, it is characterized in that using the standard industry coating technology will put preparation in order is coated on textile fabric and the fabric, dry then also set, for example pad dyeing of described standard industry coating technology, coating or spraying.
Textile fabric that---for example stenter or airflow dryer---will put 28. the manufacturing textile fabric of claim 27 and the method for the finishing agent on the fabric is characterized in that using conventional industrial equipment and fabric drying 30 to 180 seconds under 50 to 150 ℃ temperature.
29. the manufacturing textile fabric of claim 27 or 28 and the method for the finishing agent on the fabric is characterized in that according to employed polymer/cross-linking system, preferably using the reaction unit of thermal reaction apparatus and/or UV or blue ray radiation when set finishing agent layer.
30. the manufacturing textile fabric of claim 29 and the method for the finishing agent on the fabric is characterized in that thermal fixation takes place under 120 to 200 ℃, preferred 140 to 160 ℃ temperature.
31. the manufacturing textile fabric of claim 29 and the method for the finishing agent on the fabric is characterized in that chemistry anchors at fabric and solidifies and the generation of dry back by UV or blue light.
32. the manufacturing textile fabric of claim 31 and the method for the finishing agent on the fabric is characterized in that the light in the visible-range of light in the UV scope of 100nm to 400nm or 400nm to 800nm is used for set.
33. the method for claim 31 or 32 is characterized in that the finishing agent layer set under protective atmosphere based on acrylate.
34. one method in the claim 31 to 33 is characterized in that active material just joins in the finishing agent component before set.
35. the method for one manufacturing textile fabric and the finishing agent on the fabric in the claim 26 to 34, the coating that it is characterized in that prime coat is carried out prior to the coating of finishing agent layer, wherein coating contains the scourability of the prime coat of reactive group with the host system in the scourability, the especially composite fibre materials that improve host system.
36. the method for one manufacturing textile fabric and the finishing agent on the fabric in the claim 26 to 35 is characterized in that also cage shape molecule being coated on the textiles to be put in order.
37. the method for one manufacturing textile fabric and the finishing agent on the fabric in the claim 26 to 36, the finishing agent layer that it is characterized in that complete set is by polarity-protic and/or polarity-non-proton property material swelling, preferably pass through the aqueous emulsion swelling of active material, in this process, the micron pocket in the finishing agent layer loads with active material.
38. by the carrier material that is selected from textile fabric and fabric be coated in the claim 20 to 25 on the carrier material textiles that one finishing agent is formed.
39. the textiles of claim 38 is characterized in that it is designed to textiles, and at least one side has in the aforementioned claim 20 to 25 one finishing agent.
40. the textiles of claim 39 is characterized in that second side has finishing agent, described finishing agent comprises and is selected from following cage shape molecule: cyclodextrin, dendritic or glucan or its mixture.
41. the textiles of claim 40 is characterized in that second side has the finishing agent that comprises silver zeolite.
42. one textiles in the claim 38 to 41 is characterized in that it can load at least a active material, preferred oil loving active material repeatedly.
43. one textiles in the claim 38 to 42 is characterized in that it is filled with at least a active material, preferred oil loving active material.
44. the textiles of claim 42 or 43 is characterized in that described at least a active material is selected from: phenol carbonic acid, farnesol or gamma-Linolenic acid (evening primrose oil), lipophile anodyne, hormone or the vitamin of the root extract of wild marjoram or Arctium, hyoscine, cinnarizine, meclizine, nicotine, heparin, antihistaminic, diclofenac, glycerol trintrate.
45. one textiles in the aforementioned claim, the quality that it is characterized in that coated finishing agent layer is 1 to 10% with respect to the dry weight of textiles, preferred 2 to 4%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH12222004 | 2004-07-20 | ||
| CH1222/04 | 2004-07-20 | ||
| CH1797/04 | 2004-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101023213A true CN101023213A (en) | 2007-08-22 |
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ID=38710407
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580031279 Pending CN101023213A (en) | 2004-07-20 | 2005-07-18 | Dressings which can be applied several times to textile fibres and textile fabrics |
| CN2005800310793A Expired - Fee Related CN101018903B (en) | 2004-07-20 | 2005-07-18 | Finishings for textile fibres and fabrics to give hydrophobic oleophobic and self-cleaning surfaces |
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|---|---|---|---|
| CN2005800310793A Expired - Fee Related CN101018903B (en) | 2004-07-20 | 2005-07-18 | Finishings for textile fibres and fabrics to give hydrophobic oleophobic and self-cleaning surfaces |
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| DE3738140A1 (en) * | 1987-11-10 | 1989-05-18 | Hoechst Ag | URETHANE GROUPS CONTAINING DISPERSION POLYMERISES BASED ON ETHYLENICALLY UNSATURATED MONOMERERS, PROCESS FOR THEIR PREPARATION AND THEIR USE |
| DE3943466A1 (en) * | 1989-03-29 | 1991-08-14 | Hans Kaesbauer | Stacker for printed sheets - is esp. for coloured glossy paper or cardboard and has conveyor, printer, stacking lifts and mechanical connection |
| DE4412588A1 (en) * | 1994-04-13 | 1995-10-19 | Huels Chemische Werke Ag | Process for producing a temperature-dependent clouding polymer matrix |
| DE19607551A1 (en) * | 1996-02-28 | 1997-09-04 | Basf Ag | Water-absorbent, foam-like, crosslinked polymers, processes for their preparation and their use |
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Also Published As
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| CN101018903B (en) | 2011-02-16 |
| CN101018903A (en) | 2007-08-15 |
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