JPH11505888A - Molded articles with cellulose coating, impregnation or cover - Google Patents

Abstract

  (57) [Summary] Shaped articles such as fibers, yarns, spun yarns, fabrics, fleeces, knits, deposits, films, thin films, membranes, papers, etc., having a cellulose coating, impregnation or cover are described. The process used for producing such shaped bodies uses a solution of the cellulose in a tertiary amine oxide, in particular N-methylmorpholine-N-oxide, optionally further containing water. Coating, impregnation or covering.

Description

DETAILED DESCRIPTION OF THE INVENTION Molded articles with cellulose coating, impregnation or cover   The present invention provides a hollow fiber using a solution of cellulose and / or a cellulose derivative. Coating, impregnating or covering membranes in the form of fibers, flat membranes or tubular membranes The membrane treated by this method and its use.   Used for clothing purposes or industrial charges to impart specific properties to molded articles Linear shaped articles such as fibers, yarns, spun yarns or woven fabrics Conventionally, coating, impregnating or covering films, membranes, paper materials, etc. Known from.   In order not to absorb moisture, for example, the corresponding moldings are treated with a hydrophobizing agent can do. The fields of use are extremely large. Therefore, it changes the electrostatic characteristics, Adjust the coloring ability, and can change the sliding resistance or frictional resistance. The properties of a molded body made of a specific substance can be adjusted by coating Performance is very diverse.   On the other hand, the moldings may consist of various substances, of course, including coatings, There are a number of compositions that can be used to soak or cover.   Thus, for example, Textilveredlung 20 (1) 8-12 (1985) Silicone that can be used as a coating agent for flat fabrics is described. Have been.   German Offenlegungsschrift 20 59 373 describes an epoch of planar fabrics. Solutions containing thio compounds and high molecular compounds such as xy compounds and thioureas Describes how to coat fabric by treating with liquid or dispersion Have been. Polyvinyl chloride, polyacrylonitrile, polyester, polysul Such as Hong, polyether, butadiene / styrene based polymers, etc. In addition to numerous synthetic compounds, many such as ovalbumin, globulin, casein Of natural macromolecular compounds and polysaccharides such as cellulose, starch and chitin derivatives No. In addition, as described in German Offenlegungsschrift 20 59 373, Natural rubber corresponds to the natural polymer compound.   What kind of specific application using cellulose belonging to natural polymer compound It is not described in detail anywhere.   Textile Research Journal December 1988, pages 735-742, Ron fiber using viscose solution, ie, cellulose xanthate solution Covering is described, in which case the cellulose is treated with diluted sulfuric acid. Regenerate by managing This has to do with well-known environmental issues.   Amine oxide as a solvent for cellulose when producing solid cellulose moldings Can be used, for example, as described in German Offenlegungsschrift 42 44 609. Are known. The molding and spinning materials disclosed in the above specification produce fibers. Used to build.   German Offenlegungsschrift 16 940 47 discloses that one is cellulose. Dissolving at least two different polymers, which may be Describes a method for producing modified polymers by subsequent co-precipitation Have been. The modified polymer thus obtained is used to produce solid yarns and films. Can be used to build and be used in coating materials and binders Wear. Thus, for example, the solution can be peeled off to a support or the paper can be reinforced. Used as an agent.   The material applied to the membrane should generally be present in association with the membrane and the membrane is no longer used. If not used, it should be treated with the materials that make up the membrane. In this case, later During treatment, it has a significant effect, especially on environmental pollution, or requires complicated recovery methods. A well-known problem arises.   Therefore, there is no serious problem during collection , Adheres better during use of the membrane, can be applied to many substances, the properties of the membrane Hollow fibers, flat membranes or materials using materials that can vary from various perspectives Key to the possibility of coating, impregnating or covering membranes in the form of tubular membranes Request exists.   The object of the present invention is therefore to operate already without harming the environment and to recover the membrane. Adheres well to the film without causing any serious problems when adjusting the characteristics of the film in various directions. How to produce a coating, impregnation or covering of the membrane that can be knotted To provide.   The task is to convert membranes in the form of hollow fibers, flat films or tubular films into tertiary polyamides. Oxide and optionally cellulose and / or cellulose derivatives in water Solved by the method of coating, impregnating or covering with the solution of However, in this case the solution does not contain any other polymer and at 120 ° C. It has a viscosity of 1 to 20000 mPa · s as measured.   As tertiary amine oxides, preferably N-methylmorpholine-N-oxide Use The solution is advantageously used with a cellulose concentration of 1 to 5% by weight, Cellulose with a DP of 300 to 800 is particularly advantageous.   The viscosity is advantageously between 0.5 and 800 mPa · s, which is measured at 120 ° C. Is determined.   The method of the invention is advantageously used for treating cellulose membranes can do.   In an advantageous embodiment, the membrane is treated with the active substance before the treatment with the cellulose solution. Manage.   In another particular embodiment, the membrane is activated carbon prior to treatment with the cellulose composition. To process. Other advantageous methods include hydrophobic membranes, especially polyamide-66, polyester A film made of a polymer such as Chemical or physical pre-treatment before packing, impregnating or covering It is. Physical pretreatment, especially using corona discharge and plasma treatment Is suitable. As a chemical pretreatment, a treatment using a coupling agent is particularly suitable. I have.   The coupling agent in the scope of the present invention is used for adhering or fixing cellulose applied to a membrane. Is a chemical compound which results in an improvement of, i.e., chemically fixes. Document “Sila nes and other Coupling Agents ”K.L.Mittal Verlag VSP Utrecht, Niederlande For example, 1,4-bis (3-aminopropyldimethylsilane) described in Coupling agents such as (lyl) -benzene and fumaric acid are particularly suitable.   The subject of the present invention is also a hollow fiber, a flat membrane or a tube, obtainable by said method. Coated, impregnated or covered membrane in the form of a membrane It is.   The subject of the present invention is also the use of said membranes in the technical and medical fields.   In order to carry out the method of the present invention, it can be carried out in the following manner. At first Phases from cellulose, amine oxides, especially N-methylmorpholine-N-oxide A solution is prepared with the corresponding amount of water.   The concentration of cellulose in the solution can vary over a wide range. This is of course Depending on the viscosity at which the treatment of the membrane is to be carried out, the cellulose molecules used Depends on quantity. Temperature also affects.   N-methylmorpho is preferably used as the monohydrate, i.e. containing water. The preparation of the solution in phosphorus-N-oxide is the usual method of preparing the corresponding spinning solution. Ie at a temperature of, for example, about 90-140 ° C.   Solutions having a cellulose concentration in the range of 1-5% are very suitable.   In particular, the coating of the planar membrane can be performed on one or both sides. that time The coating is applied using conventional techniques, for example by spin coating (eg using a roller). ), By applying a corresponding amount of solution, for example casting and then It can be applied by scraping to a predetermined thickness. Equivalent cellulos It is also possible to pass the membrane through a bath containing a solution of the solution. This allows the membrane to be on both sides Coating or Has a completely impregnated or corresponding cover.   The thickness of the coating or cover or the degree of impregnation is The amount can be largely controlled. Other possibilities are of course equivalent in solution. Control of the cellulose concentration.   A coating in the sense of the invention is a substrate, here a continuously applied layer or In the form of a plane, in the form of intermittent planes, or in a regular or irregular manner Coated in the form of a dotted or planar coating material Is to apply a material.   Cellulose in the meaning of the invention can be of various forms, i.e. of various origins and species. Cellulose having various degrees of polymerization, such as cotton lint, cotton fiber, microcrystalline cellulose And cellulose obtained from wood. The degree of polymerization is 150-7000 May be between. Higher or lower values are not excluded. Various degrees of polymerization Or mixtures of origin can be used.   Cellulose is used alone or in the form of a mixture with a cellulose derivative. Use as long as it is soluble or finely dispersible in tertiary amine oxides. Can be.   Modifies the surface of the membrane when treating a membrane where the coating may be one or both sides That can be Different effects can be achieved by selecting the amount to be applied. Therefore, living It is possible to adjust the compatibility, the permeability and the separation limit (cutoff). Sparse Aqueous membranes can be made hydrophilic by coating one side on one side. Also Of course, both surfaces can be hydrophilized.   It is preferable that the membrane is sufficiently dry before coating Moist surfaces cause flocculation of cellulose dissolved in tertiary amine oxides This is because there are times. As well as working with mostly dry membranes The cellulose does not generally adhere to the support during the corresponding setting.   The processing time, i.e., the time that the membrane is in contact with the processing solution, depends on the cellulose in the solution. Obviously, the dissolved solvent is not long enough to cause adverse degradation of the membrane It is.   Thus, coatings on membranes, generally performed at elevated temperatures, such as 90-140 ° C, Immediately after coating, impregnation or covering, the treated membrane is Baking bath, e.g. alcohol, acetone, water or a mixture, but advantageously in water Extraction of tertiary amine oxide, especially N-methylmorpholine-N-oxide It is necessary to.   Another possibility to avoid too strong dissolution or further decomposition of the membrane is to treat the treated membrane Is to cool rapidly . At that time, the N-methylmorpholine-N-oxide solidifies, and the treated film is further decomposed. May eat. In that case, the amine oxide can be extracted at a later point in time. Wear.   Therefore, when processing a film that dissolves in tertiary amine oxide, for example, at 120 ° C. When processing at, the processing time should be about 2 to 60 seconds.   It is obvious that the processing time depends on the film thickness.   However, in the case of a film made of a substance that does not dissolve in tertiary amine oxide, This degree of this precaution is not necessary.   On the other hand, when just treating a cellulose membrane, a certain dissolution of the membrane surface takes place. A particularly tight bond between the membrane and the coated cellulosic material is achieved during coagulation. This is because the coating, impregnated surface or cover is tightly bonded to the membrane is there.   If the coated film is to be cooled rapidly after coating, Increase the viscosity of the coating so that the unpacking process is interrupted, while freezing the shape .   Depending on the form and method of how and when to extract the solvent, The structure of the coating and thus, for example, the permeability of the coating to water be able to. If extraction is performed immediately after cooling, It has generally been found that the permeability is higher.   Care must be taken that the membrane to be further treated can be wetted by the cellulose solution. No. This is the case with cellulose-based membranes, which are generally already Are no longer wettable by other chemicals and are being treated. You. In this case, the coating is performed, for example, by washing with water or another solvent. The material to be clothed is removed, the membrane is dried and only afterwards treated with a cellulose solution Preferably.   Physical surface treatment, such as corona discharge, for the wetting ability of the membrane with cellulose solution Or by plasma treatment or by chemical treatment, for example using a coupling agent It can be significantly increased by processing.   For cellulose membranes, the adhesion or surface penetration of Pretreating the support with ammonium, ammonia or tertiary amine oxide Can be improved.   First the membrane is treated with an active substance, such as an adsorbent, an antistatic agent, etc. It is also possible to carry out pretreatment with a soluble substance. The wettability of the membrane is not reduced to such an extent that treatment with Should be considered.   The membrane according to the invention can be used in gaseous or liquid systems in the medical and technical fields. Can be used for substance separation Depending on the structure, for example, nanofiltration, ultrafiltration, microfiltration Are suitable. Separate gas or purify gas using the treated membrane can do.   If using an active substance that is applied to the molded body before processing, The environment can be adjusted and discharged.   On the other hand, the bound agent interacts with the substance without leaving the coated membrane And discharges from the surrounding environment, thus adsorbing gases, for example, and ions from aqueous systems. Alternatively, the organic groups can be removed from the aqueous medium.   The present invention will be described in detail by the following examples.   Example 1   Production of cellulose solution   1073 g of NMMO / water (76% NMMO), cellulose (DP = 625, containing 40 g of water (5% of water) and 1.7 g of stabilizer (propyl gallate) in a container Charge and heat to 90 ° C. The dispersion is stirred for about 15 minutes and then excess water ( 130 g) are separated at 120 ° C. under vacuum. After separating the water and degassing the solution A 3.5% cellulose solution is obtained. Filter the solution before coating.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B05D 7/24 302 B05D 7/24 302C (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR , GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG) ), AP (KE, LS, MW, SD, SZ, UG), UA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AU, BB, BG, BR , CA, CN, CZ, EE, FI, GE, HU, IS, JP, KG, KP, KR, LK, LR, LT, LV, MD, MG, MK, MN, MX, N , NZ, PL, RO, SG, SI, SK, TR, TT, UA, US, UZ, VN

Claims (1)

[Claims] 1. Membranes in the form of hollow fibers, flat membranes or tubular membranes are tertiary amine oxide and Optionally, using a solution of cellulose and / or cellulose derivative in water Coating, impregnation or covering, but in this case The liquid does not contain any other polymer and is 1-2000 mP measured at 120 ° C cellulose and / or cellulose having a viscosity of as A method of coating, impregnating or covering a membrane with a solution of a derivative. 2. Using N-methylmorpholine-N-oxide as tertiary amine oxide The method of claim 1 wherein: 3. 3. The method according to claim 1, wherein a 1 to 5% by weight solution of cellulose is used. . 4. 4. The method according to claim 3, wherein cellulose having a DP of 300 to 800 is used. . 5. The method according to claim 1, wherein a solution having a viscosity of 0.5 to 800 mPa · s is used. Method. 6. Use cellulose membrane to coat, impregnate or cover A method according to any one of claims 1 to 5. 7. Before coating, impregnating or covering 7. The method according to claim 1, wherein the membrane is treated with an active substance. 8. The method according to claim 7, wherein the membrane is treated with activated carbon before coating. 9. Claims 1 using a chemically or physically pretreated hydrophobic membrane The method according to any one of claims 1 to 7. 10. Uses a film that has been physically pretreated by corona discharge or plasma treatment The method of claim 1 wherein 11. Use of hydrophobic membranes that have been chemically pre-treated with coupling agents 10. The method according to claim 9, wherein 12. It can be produced by the method according to any one of claims 1 to 11, Coated or impregnated furnaces in the form of hollow fibers, flat or tubular membranes Or covered membrane. 13. 13. The membrane of claim 12 for separating substances in gaseous or liquid systems. use. 14． Use of a membrane according to claim 12 for controlled release of an active substance.