EP0740007A2 - Verfahren zur Behandlung von Textilien - Google Patents

Verfahren zur Behandlung von Textilien Download PDF

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Publication number
EP0740007A2
EP0740007A2 EP95117738A EP95117738A EP0740007A2 EP 0740007 A2 EP0740007 A2 EP 0740007A2 EP 95117738 A EP95117738 A EP 95117738A EP 95117738 A EP95117738 A EP 95117738A EP 0740007 A2 EP0740007 A2 EP 0740007A2
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EP
European Patent Office
Prior art keywords
textile finish
textile
mixing
water
raw
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP95117738A
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English (en)
French (fr)
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EP0740007A3 (de
Inventor
Jack L. Anderson
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Henkel Corp
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Henkel Corp
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Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP0740007A2 publication Critical patent/EP0740007A2/de
Publication of EP0740007A3 publication Critical patent/EP0740007A3/de
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/08—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating from outlets being in, or almost in, contact with the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation
    • D06B23/205—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation for adding or mixing constituents of the treating material

Definitions

  • the present invention generally relates to an in-line process for continuously preparing textile finish compositions and treating textiles therewith More particularly, a process is provided whereby a predetermined amount of a textile finish composition having a specific formulation can be prepared on an as-needed basis for treatment of textile materials.
  • compositions referred to as "spin finishes” are usually applied to textile fibers after extrusion. These or other finishes may be applied to yarn prior to knitting or winding, and to fiber tows prior to or at the time of crimping, drying, cutting, drawing, roving, and spinning, or to staple fibers prior to carding.
  • the application of lubricants onto fibers prior to carding and subsequent textile operations such as yarn manufacture, preparation of nonwoven webs or processing of continuous filament yarns after the fiber spinning process are commonly called secondary or over-finishes Such finishes provide lubrication, prevent static build-up, and afford sufficient cohesion between adjacent fibers.
  • finish compositions can also be applied to tow, yarn, or cut staple by spraying.
  • Satisfactory finish compositions must fulfill a number of requirements in addition to providing desired lubricating and antistatic effects. For example, they should be easy to apply (and to remove if desired), they should have good thermal and chemical stability, they should not adversely affect the physical or chemical properties of the fibers to which they are applied aid they should aid the subsequent processes to which the treated fibers are subjected, they should not leave residues on surfaces or cause toxic fumes or undesirable odors, they should provide for rapid wetting of fiber surfaces, they should be water-soluble or emulsifiable or solvent-soluble, they should have good storage stability, they should be compatible with sizes, nonwoven binders and other fiber treatments, they should not attract soil or cause color changes to the fibers, they should not interact with frictional elements used in texturizing and they should not be corrosive to machine parts.
  • U.S. Patent 4,027,617 discloses a finish for acrylic fiber consisting of an alkyl phenol ethoxylated with 40 to 200 moles of ethylene oxide, an amine salt of hydrogenated tallow-alcohol phosphate, and a mixture of mineral oil, an ethoxylated aliphatic monohydric alcohol, and the amine-neutralized reaction product of an ethoxylated aliphatic monohydric alcohol phosphate.
  • U.S. Patent 4,027,617 discloses a finish for acrylic fiber consisting of an alkyl phenol ethoxylated with 40 to 200 moles of ethylene oxide, an amine salt of hydrogenated tallow-alcohol phosphate, and a mixture of mineral oil, an ethoxylated aliphatic monohydric alcohol, and the amine-neutralized reaction product of an ethoxylated aliphatic monohydric alcohol phosphate.
  • Patent 3,997,450 relates to a finish composition for synthetic fibers such as polyamides and polyesters, consisting essentially of a lubricant selected from a mono- or diester of an aliphatic carboxylic acid with a monohydric aliphatic alcohol, or a refined mineral, animal or vegetable oil; an emulsifier containing up to 50 moles of alkylene oxide per mole of ester, alcohol, or amide wherein the reactive hydroxyl sites of the emulsifiers contain deactivating and cap groups; and an alkali salt of a dialkyl sulfosuccinic acid.
  • a lubricant selected from a mono- or diester of an aliphatic carboxylic acid with a monohydric aliphatic alcohol, or a refined mineral, animal or vegetable oil
  • the emulsifiers employed include soaps, glycerol fatty acid esters, sorbitan and polyoxyethylene sorbitan esters, polyglycerol esters, polyoxyethylene esters or ethers, polyoxyethylene polyol ether esters, polyoxyethylene amines and amides, partial polyol ester ethoxylates, sulfated vegetable oils, sulfonated hydrocarbons, and the like.
  • a fiber finish is to provide fiber to metal lubrication and fiber to fiber cohesion, as well as reduce static electricity.
  • Another example involves a slit film or ribbon type yarn intended for woven carpet backing for tufted carpets. During its manufacture, good wetting of the fiber surface by the finish and moderate frictional coefficients are required. For tufting, however, relatively low fiber to metal friction is a very important feature because of the action of tufting needles on the backing fabric.
  • low fiber to fiber friction is a highly desirable feature of continuous filament yarns used in cordage applications which involve twisting and plying to form compact structures which have a large amount of fiber to fiber contact. Low friction is desirable since it is generally associated with high flex resistance, high energy absorption and therefore, long life.
  • a different area of fiber-to-fiber friction is concerned with continuous filament yarns. This may be illustrated by some examples within the fiber manufacturing plant, i.e., package building in spinning and filament drawing or tow drawing are the major steps where the fiber-to-fiber friction is of critical importance.
  • yarn delivery in coning, stitch formation in knitting, filament damage in braiding, strength and elongation in cordage, slippage of weave in fabric, yarn-to-fabric friction in sewing are some of the areas where yarn-to-yarn friction is important.
  • Textile finish compositions such as those described above are typically formulated by the end-user. Suppliers and manufacturers provide the end-user with the raw textile finish components needed to formulate the finish composition. Prior to their application onto textile substrates, the raw textiles finish components must first be formulated and/or diluted to a specific concentration for a particular application and/or mixed with auxiliary components such as emulsifiers, anti-static agents, etc..
  • auxiliary components such as emulsifiers, anti-static agents, etc.
  • a batchwise process is most commonly employed to formulate the textile finish compositions. This process involves introducing the raw textile finish components into a large vessel, and then mixing them with water along with any additional auxiliary components which may be required. The contents of the vessel and mixed by mechanical means such as by the use of a propeller-type mixing device or an auger.
  • the disadvantages associated with the use of this type of batchwise process for formulating textile finish compositions are as follows.
  • the present invention is generally directed to a process for treating textile substrates.
  • the present invention eliminates the need for the batchwise formulation of textile finish compositions prior to their application onto textile substrates.
  • the sole figure is a schematic view of one embodiment of an apparatus which may be employed in the invention for the in-line formulation of textile finish compositions in which multiple raw textile finish components and water are introduced into an interfacial surface generator, through multiple inlet ports, where they are subsequently statically mixed and discharged as a newly formulated textile finish composition through the outlet conduit.
  • the present invention provides for the in-line formulation of a textile finish composition on an as-needed basis, and its subsequent application onto a textile substrate.
  • a mixing apparatus comprising an interfacial surface generator wherein the components are intimately mixed in order to produce a formulated finish composition of predetermined quantity, concentration and characteristics prior to contact with a textile substrate.
  • the principal components of the mixing apparatus 1 employed to carry out the present invention include a water inlet port 2a and raw textile finish component inlet ports 2b and 2c for introducing water and raw textile finish components to be formulated into a textile finish composition, an interfacial surface generator 6 for statically mixing the water and raw textile finish components, an outlet port 9 for dispensing the formulated textile finish composition and a control unit 7 for controlling the operation of the apparatus 1.
  • water is introduced to the apparatus from a source, not shown, through inlet port 2a.
  • Raw textile finish components are similarly fed from individual sources, not shown, through inlet ports 2b and 2c.
  • Valves 3a, 3b and 3c are used to open and close inlet ports 2a, 2b and 2c so that water and the various raw textile finish components may be introduced into the interfacial surface generator 6 through fluid port 5.
  • pumps 4a and 4b are used to meter the raw textile finish components through inlet ports 2b and 2c and they are combined, along with the water, into a single fluid stream and fed through fluid port 5 into the interfacial surface generator 6.
  • the interfacial surface generator 6 employed in the present invention is well known in the art.
  • U.S. Patent 3,583,678, hereby incorporated by reference discloses a typical interfacial surface generator used for static mixing of fluids wherein a fluid stream is divided into a plurality of substreams which are then recombined, divided, repositioned, and recombined again until a desired degree of mixing is obtained.
  • These types of interfacial surface generators are capable of providing a degree of mixing that is a function of the number of static mixing elements (n) employed. Each element individually divides and mixes the liquid stream four times. Consequently, each additional element (n) employed increases the degree of mixing on the order of 4 n .
  • Other examples of interfacial surface generators known in the art, and also incorporated herein by reference are disclosed in U.S. Patent 3,358,749, 3,404,869 and 3,652,061.
  • valve 8 is opened so that the textile finish composition may be discharged through outlet port 9.
  • the freshly formulated textile finish composition is then ready for contact with a textile substrate.
  • control unit 7 can be employed in operative connection with the apparatus to perform all of these functions.
  • the type of control unit 7 employed by the present invention is well known in the art.
  • the control unit 7 is capable of being programmed so that predetermined amounts of water and various raw textile finish components may be measured and subsequently introduced into the interfacial surface generator 6.
  • the control unit 7 can also be programmed to provide varying degrees of mixing for numerous types of textile finish compositions.
  • all of the operating components of the apparatus 1 are electronically controlled, with variables such as amounts of water and raw textile finish components to be admixed and degrees of mixing being programmed into and controlled by control unit 7.
  • the primary components of most textile finish compositions include a lubricant, emulsifiers known in the art such as ethoxylated C 12-18 fatty alcohols, an anti-jelling agent and an anti-static agent. It is oftentimes highly desirable to also include a wetting agent to aid in the penetration, spread and adherence of the textile finish composition onto the textile substrate.
  • the textile composition is typically applied onto the textile substrate as an aqueous emulsion.
  • the lubricant component of the fiber finish composition is preferably selected from the group consisting of ethoxylated fatty acids such as the reaction product of ethylene oxide with pelargonic acid to form PEG 300 monopelargonate (Emerest® 2634) and PEG 400 monopelargonate (Emerest® 2654), the reaction product of ethylene oxide with coconut fatty acids to form PEG 400 monolaurate (cocoate) (Emerest® 2650) and PEG 600 monolaurate (Emerest® 2661), and the like.
  • ethoxylated fatty acids such as the reaction product of ethylene oxide with pelargonic acid to form PEG 300 monopelargonate (Emerest® 2634) and PEG 400 monopelargonate (Emerest® 2654
  • the reaction product of ethylene oxide with coconut fatty acids to form PEG 400 monolaurate (cocoate) (Emerest® 2650) and PEG 600 monolaurate (Emerest® 2661)
  • the lubricant component can also be selected from non-water-soluble materials such as synthetic hydrocarbon oils, alkyl esters such as tridecyl stearate (Emerest® 2308) which is the reaction product of tridecyl alcohol and stearic acid, and polyol esters such as trimethylol propane tripelargonate (Emery® 6701) and pentaerythritol tetrapelargonate (Emery® 2484), as well as oxa-acid esters, may also be employed.
  • any lubricant based on synthetic, mineral, animal or vegetable oil typically known in the art for use as a lubricant in textile finish compositions may be employed in the present invention.
  • the textile finish of this invention is emulsifiable and capable of forming a stable emulsion with water.
  • stable emulsion it is meant that the emulsion is stable at the time of application of the textile finish composition to a textile substrate. This is meant to include both oil-in-water and water-in-oil finishes which, typically, are mixed well prior to their application and then applied via various applicators from a storage tank or the like and thus the textile finish composition in the form of an emulsion must traditionally be stable for extended time periods.
  • textile finish compositions in the form of a highly dispersed emulsion can be prepared in the exact amount needed for a particular application, in-line with the application process, and on an as-needed basis.
  • the present process reduces the concentration of emulsifier required to maintain a stable emulsion. Hence, since less emulsifier is needed, this translates into a significant savings in production costs.
  • Anti-static agents function by either reducing the charge generation or by increasing the rate of charge dissipation. Most antistats operate by increasing the rate of dissipation and rely on atmospheric moisture for their effectiveness.
  • a hydrophobic fiber such as polypropylene depends on an antistat coating to impart high surface conductivity for charge dissipation.
  • the antistatic agent may comprise any suitable anionic, cationic, amphoteric or nonionic antistatic agent.
  • Anionic antistatic agents are generally sulfates or phosphates such as the phosphate esters of alcohols or ethoxylated alcohols.
  • Cationic antistatic agents are typified by the quaternary ammonium compounds and imidazolines which possess a positive charge. Examples of nonionics include the polyoxyalkylene derivatives. The anionic and cationic materials tend to be more effective antistats.
  • Preferred anionic antistatic agents for use herein include an alkali metal salt, e.g., potassium, of a phosphate ester such as commercially available from Henkel Corporation, Mauldin, South Carolina, under the tradenames Tryfac® 5559 or Tryfac® 5576.
  • alkali metal salt e.g., potassium
  • a phosphate ester such as commercially available from Henkel Corporation, Mauldin, South Carolina, under the tradenames Tryfac® 5559 or Tryfac® 5576.
  • Preferred nonionic antistatic agents include ethoxylated fatty acids (Emerest® 2650, an ethoxylated fatty acid), ethoxylated fatty alcohols (Trycol® 5964, an ethoxylated lauryl alcohol), ethoxylated fatty amines (Trymeen® 6606, an ethoxylated tallow amine), and alkanolamides (Emid® 6545, an oleic diethanolamine).
  • Emerest® 2650 an ethoxylated fatty acid
  • ethoxylated fatty alcohols Trycol® 5964, an ethoxylated lauryl alcohol
  • ethoxylated fatty amines Trymeen® 6606, an ethoxylated tallow amine
  • alkanolamides Emid® 6545, an oleic diethanolamine
  • the amount of antistatic agent present in the finish composition is generally from about 5 to about 30 weight percent when there is a possibility that static electricity may be a problem. In some cases less might be required, for example, for continuous filament yarns which are interlaced or for a winding operation. In other cases such as for staple fiber processing, larger amounts of antistatic agent may be required.
  • a surfactant and/or a solvent be used as a wetting agent in the composition.
  • the surfactant and/or solvent acts to ensure that the particular textile finish composition to which it is added is evenly and effectively distributed throughout the textile substrate.
  • a particularly preferred wetting agent is an alkylpolyglycoside of formula I R 1 O(Z) a (I) wherein R 1 is a monovalent organic radical having from about 6 to about 30 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; and a is a number having a value from 1 to about 6.
  • the textile finish composition may be applied onto a textile substrate according to a variety of known procedures.
  • the polymer is melted and extruded through spinnerette holes into filaments which are cooled and solidified in an air stream or water bath.
  • the filaments contact a textile finish composition applicator which can be in the form of a kiss roll rotating in a trough.
  • the amount of active finish composition applied to the filaments can be controlled by the concentration of textile finish composition in the solution or emulsion and the total wet pick-up.
  • positive metering systems may be used which pump the finish composition to a ceramic slot which allows the finish composition to contact the moving filaments.
  • Textile finish compositions can also be applied onto textile substrates by spraying.
  • the textile substrate which now has a coating of textile finish composition moves forward into any of several processes.
  • the amount of finish composition to be applied onto a synthetic filament is also dependent on the end product of the filament yarn. If staple fiber is the desired product, the filament bundles are combined into large tows, oriented by stretching, crimped, and cut into short lengths for processing on textile equipment to ultimately make yarn or nonwoven webs.
  • the present process is employed to formulate spin finish emulsions, in-line with a textile substrate application process, on an as-needed basis.
  • the primary components of a spin finish are a lubricant, an emulsifier, an anti-static agent and water which, when combined, form an emulsion.
  • Predetermined amounts of these components are combined and mixed so as to formulate a spin finish composition having a specific concentration required for an end-user's particular application process. Varying concentrations of spin finishes in turn require varying degrees of mixing so that a desired degree of dispersion of the raw textile finish components and water is obtained.
  • the newly formulated textile finish compositions may be applied to virtually any textile substrate including glass, cellulosics such as acetate, triacetate, rayon, non-cellulosics such as acrylics, modacrylic, nylon, aramid, olefins such as polyethylene and polypropylene, polybenzimidazole, polyesters such as polyethylene terephthalate and polybutylene terephthalate or copolyesters thereof, saran, spandex and vinyon.
  • cellulosics such as acetate, triacetate, rayon
  • non-cellulosics such as acrylics, modacrylic, nylon, aramid, olefins such as polyethylene and polypropylene, polybenzimidazole
  • polyesters such as polyethylene terephthalate and polybutylene terephthalate or copolyesters thereof, saran, spandex and vinyon.
  • any number of raw textile finish components or auxilliaries such as surfactant blends/dispersions of waxy lubricants, for example fatty amides, fatty esters, oxidized polyethylene, and the like, needed for a particular textile finish composition may be employed.
  • a spin finish composition for fiber and textile applications was prepared having the following formulation.
  • Component % by weight (a) STANTEX® 1910-G 10 (b) water 90
  • a spin finish composition for fiber and textile applications was prepared having the following formulation.
  • Component % by weight (a) STANTEX® 1910-G 10 (b) water 90
  • Example 1 The components listed above were mixed, at a temperature of 50°C, using conventional agitation to form a spin finish.
  • the textile spin finish compositions of Example 1 and Comparative Example 1 were then analyzed to determine their aesthetic appearance and degree of mixing.
  • a photoelectric colorimeter, clinical model, catalog number 76-500-000, available from MANOSTAT® Inc., 519 Eighth Ave., New York, NY was used to measure the degree of mixing achieved by the present process versus a conventional mixing process.
  • Tale 1 summarizes the results obtained. Appearance Photoelectric Colorimeter Value Example 1 Translucent 60 Comparative Example 1 Opaque 870
  • Table 1 shows that by employing the present process of mixing textile and spin finishes, a significantly increased degree of mixing is obtained, as compared to conventional mixing techniques. Moreover, due to the significantly enhanced degree of mixing obtained with limited expenditure of manpower, as compared to conventional mixing processes, the present process allows for the in-line mixing of textile and spin finishes on an as-needed basis.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment Of Fiber Materials (AREA)
EP95117738A 1995-04-18 1995-11-10 Verfahren zur Behandlung von Textilien Withdrawn EP0740007A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42318895A 1995-04-18 1995-04-18
US423188 1995-04-18

Publications (2)

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EP0740007A2 true EP0740007A2 (de) 1996-10-30
EP0740007A3 EP0740007A3 (de) 1998-01-07

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EP95117738A Withdrawn EP0740007A3 (de) 1995-04-18 1995-11-10 Verfahren zur Behandlung von Textilien

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EP (1) EP0740007A3 (de)
KR (1) KR960037917A (de)
CN (1) CN1133918A (de)
TW (1) TW356482B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1039011A2 (de) * 1999-03-25 2000-09-27 Barmag AG Vorrichtung und Verfahren zum Auftragen eines Präparationsmittels auf einen laufenden Faden
US6405759B1 (en) 1997-08-05 2002-06-18 Owens Corning Composites Sprl Apparatus for the continuous preparation of glass fiber sizing compositions
CN113929099A (zh) * 2021-10-27 2022-01-14 赣州海盛钨钼集团有限公司 一种超细碳化钨粉末的制备方法
CN116971114A (zh) * 2023-09-20 2023-10-31 于都欧迪亚针织有限公司 一种毛衣生产用加湿设备

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3358749A (en) 1966-07-22 1967-12-19 Dow Chemical Co Interfacial surface generator and method of preparation thereof
US3404869A (en) 1966-07-18 1968-10-08 Dow Chemical Co Interfacial surface generator
US3583678A (en) 1969-09-15 1971-06-08 Dow Badische Co Interfacial surface generators
US3652061A (en) 1971-03-04 1972-03-28 Dow Chemical Co Interfacial surface generator and method of preparation thereof
US3997450A (en) 1972-04-10 1976-12-14 Fiber Industries, Inc. Synthetic fibers of enhanced processability
US4725371A (en) 1985-01-29 1988-02-16 Celanese Corporation Partially oriented polyester yarn emulsion finish with elevated pH

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5236624A (en) * 1987-03-16 1993-08-17 Exxon Chemical Patents Inc. Dispersions and emulsions
DE4041362C1 (de) * 1990-12-20 1992-06-04 Ramisch Kleinewefers Gmbh, 4150 Krefeld, De
US5232742A (en) * 1992-05-15 1993-08-03 Bridgestone/Firestone, Inc. Spin finish composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404869A (en) 1966-07-18 1968-10-08 Dow Chemical Co Interfacial surface generator
US3358749A (en) 1966-07-22 1967-12-19 Dow Chemical Co Interfacial surface generator and method of preparation thereof
US3583678A (en) 1969-09-15 1971-06-08 Dow Badische Co Interfacial surface generators
US3652061A (en) 1971-03-04 1972-03-28 Dow Chemical Co Interfacial surface generator and method of preparation thereof
US3997450A (en) 1972-04-10 1976-12-14 Fiber Industries, Inc. Synthetic fibers of enhanced processability
US4725371A (en) 1985-01-29 1988-02-16 Celanese Corporation Partially oriented polyester yarn emulsion finish with elevated pH

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6405759B1 (en) 1997-08-05 2002-06-18 Owens Corning Composites Sprl Apparatus for the continuous preparation of glass fiber sizing compositions
EP1039011A2 (de) * 1999-03-25 2000-09-27 Barmag AG Vorrichtung und Verfahren zum Auftragen eines Präparationsmittels auf einen laufenden Faden
EP1039011A3 (de) * 1999-03-25 2001-04-11 Barmag AG Vorrichtung und Verfahren zum Auftragen eines Präparationsmittels auf einen laufenden Faden
KR100665546B1 (ko) * 1999-03-25 2007-01-09 바마크 악티엔게젤샤프트 윤활장치 및 윤활제를 가하는 방법
CN113929099A (zh) * 2021-10-27 2022-01-14 赣州海盛钨钼集团有限公司 一种超细碳化钨粉末的制备方法
CN116971114A (zh) * 2023-09-20 2023-10-31 于都欧迪亚针织有限公司 一种毛衣生产用加湿设备
CN116971114B (zh) * 2023-09-20 2024-04-02 于都欧迪亚针织有限公司 一种毛衣生产用加湿设备

Also Published As

Publication number Publication date
TW356482B (en) 1999-04-21
EP0740007A3 (de) 1998-01-07
KR960037917A (ko) 1996-11-19
CN1133918A (zh) 1996-10-23

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