CN1367721A - Process for hydrophobic treatment of water vapour permeable substrates - Google Patents

Process for hydrophobic treatment of water vapour permeable substrates Download PDF

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Publication number
CN1367721A
CN1367721A CN99816892.0A CN99816892A CN1367721A CN 1367721 A CN1367721 A CN 1367721A CN 99816892 A CN99816892 A CN 99816892A CN 1367721 A CN1367721 A CN 1367721A
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CN
China
Prior art keywords
coating
base material
aforementioned arbitrary
monomer
water vapour
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Pending
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CN99816892.0A
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Chinese (zh)
Inventor
萨斯瓦蒂·达塔
保罗·阿马特·雷蒙德·杰勒德·弗朗斯
阿尔谢尼·瓦莱雷维赫·拉多梅谢利斯基
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Publication of CN1367721A publication Critical patent/CN1367721A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

The present invention relates to a process, preferably a continuous process, of coating a substrate, which allows water vapour and preferably air permeation, with a hydrophobic coating. The process preferably uses a thin film vacuum condensation step to create a monomer coating which is cured in situ after the coating. The process has the benefit of allowing continuous operation and providing an alternative to existing processes for hydrophobic coating. The substrates are coated such that the water vapour permeation sites are not blocked by the coating to maintain the desired breathability. The static water contact angle on the surface of such substrates is more than 95°. Such substrates are preferably employed in absorbent articles such as diapers, incontinence products, underarm sweat pads, sanitary napkins, catamenials, pantiliners, breast pads, shoe inserts of bandages or alternatively in protective garments such as gloves or rain coats for which water vapour transmission in particular from the inside to the outside is highly desirable.

Description

The dewatering process method of water vapour permeable substrates
Invention field
The present invention relates to a kind of method that on the base material that can make vapor permeation and preferred air penetration, is coated with hydrophobic coating, more preferably relate to a kind of continuous coating process.This method preferably adopts film vacuum condensation step to produce the monomer coating, and this monomer coating can be solidified on the spot after the coating.The advantage of this method is and can works continuously, and the selection of the method that substitutes existing coating hydrophobic coating is provided.Base material after coating, coating is not blocked the break of steam, makes it still keep required gas permeability.The contact angle of Static Water is greater than 95 ° on this coated substrate.This base material is preferred on the adsorbable goods, as diaper, incontinence product, sweat pad under armpit, sanitary napkin, product for women menstruation, underpants, chest pad, shoe-pad or bandage, or the substitute of protective clothess such as gloves, raincoat, in these goods, be starved of steam and be penetrated into the outside especially internally.
Background of invention
For example, US 3,498, instructed in 527 and adopted as paraffin or polyethylene as waterproof coating, can obtain the cardboard liquid container of waterproof.Similarly method also has US 2,708, waterproof paper water glass in 645 and the paper sundry goods bag among the US 3,212,697.At US 3,597, the coating that discloses the product that is coated with polyalcohols-polyacetals on paper in 313 can strengthen the interim wet strength of paper, and this coating process can be used for producing disposable cleaning clothing item.US 3,078, disclose a kind of disposable sanitary napkin in 849, and it is that protection liquid liner or similar material are the adsorption layer of liner that this sanitary napkin contains with the polyvinyl alcohol, and this gasket material repels water and final solubilized water at first.By regulating the water-fast degree of controllable thickness system of liner, control the service life of sanitary napkin thus.Because manufacturer or user can not predict the necessary service life of sanitary napkin, therefore consider all possibilities, liner must have enough thickness.US 3,542, disclosed the adsorptivity sanitary napkin that the fibre sheet handled by the fluorinated polymer coating is formed in 028.US 3,559, and 650 have instructed a kind of preparation method of sanitary napkin, contain two disposable sorbing materials that separated by a waterproof membrane in this sanitary napkin, and waterproof membrane is very thin, in case in use two-layer sorbing material fragmentation, then waterproof membrane is enough to support itself.
With the principle that is coated with waterproof material from the teeth outwards similarly is that the surface of base material and another kind of material are reacted, so that form a kind of product with water resistance on substrate surface.For example, US 2,130,212 and US 3,137,540 in instructed material to react with other material to improve its water resistance as polyalcohols.At US 3,137, also instructed in 540 and can improve its water resistance after adopting the water-soluble emulsion of aldehyde to handle the polyvinyl alcohol product.US 3,626, instructed the employing polyvinyl alcohol to prepare disposable diaper in 943, and a side of diaper and formaldehyde react and can have water-proof function.Also there are some defectives in the coating process of these response types, and reaction needed is carried out at aqueous phase, and is not only very complicated, and needs relatively large reaction reagent.Utilize chemical reaction on the spot to form the method for surface waterproofing coating, major part is carried out in liquid phase, and some gas phase treatment methods are disclosed in US 2,306, and 222, among US 2,961,388 and the US 3,017,290.At USSR Patent1, the grease proofing processing method of a kind of textile water proof is disclosed in 158,634, be included in the inorganic gas phase, carry out plasma treatment under the glow discharge, in gas phase, adopt fluoro-acrylate monomer to handle then.At US 4,188, disclose the plasma polymerisation method of another kind of acquisition film formerly in 426, be included in the glow discharge of Freon C318 or perfluoroethane and handle, improved hydrophobic performance organic and that inorganic substrate (for example polyethylene film, metal) is surperficial so that reduces coefficient of friction.Yet above-mentioned disclosed method all can not reach the water resistance of coating process of the present invention disclosed herein.
Adopting the fluorocarbon film to the method that metal, polymer and other base materials carry out the plasma coating, also is known in the prior art.For example US 4,869, film, sheet, band, plate and difform goods that plastics, metal or other material are made are disclosed in 922, continuous (that is: not regulating) radio frequency (RF) glow discharge sediment of fluorocarbon is provided, to form thin fluorocarbon coating, between this coating and base material, do not contain other material.And point out to have good tack between this coating and its substrates coated, tight, evenly, continuously, and form according to its surface chemistry, but the wettability of control surface.Above-mentioned patent is described does not regulate, the characteristic of the coating of continuous plasma method gained is that Static Water contact angle (WCA) is less than 120 °.
US 5,328, a kind of surface waterproofing of textiles or paper and method of grease proofness of giving disclosed in 576, it comprises that at first (in the presence of the steam) carries out preliminary treatment to material in the Low Pressure Oxygen plasma atmosphere, in this handles the storehouse, under the high frequency glow discharge, carry out the plasma polymerization of methane then.This method can not obtain continuously and coating enduringly, and the WCA of its gained coating is greater than 120 °.
US 5,262, disclose in 208 the paper file that needs archives to preserve is carried out gas plasma to handle, to form the method for thin polymer diaphragm.Its processing time is 30-3600 second.Another kind method is the coating of processing to obtain to approach of fabric being carried out the short time.At US 4,842,893 and US 4,954,371 in disclose and a kind ofly substrate surface is carried out high-speed coating obtain complete uniform adhesive coatings, and adopt the monomer methods of the vapor deposition of electron beam actinic radiation-curable multi-layer capacitor.US4 discloses in 842,893 and has comprised in the high-speed coating method that flash distillation system and electronic beam curing handle.Disclosed electron beam content is hereby incorporated by in above-mentioned two patents.U.S. west room Science ﹠ Technology Center has reported that also electron beam is coated on other application in the electronics industry.(Adv.Mat.Newsletter rolled up the 4th page of the 9th phase in 1991 the 13rd).
Though past people has adopted different method for waterproofing, method, the plasma coating process that is coated with in monomer solution coating and the method for solidifying, the washing process for example, but still need provide coating process under a kind of high production speed, waterproof coating that obtain approaching, preferably can be lasting, and the performance of applied base material for example elasticity, quality, comfortableness and gas permeability etc. change very little.The present invention combines the advantage of the above-mentioned high-velocity electron beam coated substrate method of mentioning, and the benefit that is used to produce the goods with persistence waterproof coating.
Therefore, though employed material is well known in the art in the present invention practice, and also known its be used for waterproof coating, and the present invention adopts electron beam treatment then to provide a kind of attractive selection to existing method in hydrophobic coating.
Summary of the invention
On the one hand, the invention provides a kind of high-speed vacuum coating process, its adopt one movably supporter place cylinder in the vacuum storehouse on base material, to prepare lasting and thin waterproof coating as one.In the temperature range of the material condensation of having evaporated that the temperature maintenance on supporter surface is deposited in can making the vacuum storehouse, this material is a kind of curable monomer with lower molecular weight, adopts flash vessel can produce monomer vapor.With the metering of the curable monomer of aequum send into heating the flash vessel system evaporate, then by it being sent on the base material that is positioned at cylinder, and at the surface condensation of base material as pressure in it itself.According to method of the present invention, again base material is sent into the place that to implement to solidify, for example the energy of divergent bundle, UV treatment or be exposed under the electromagnetic field.Also curable monomer can be sent into plasma area (high voltage discharge field) in addition and produce free radical.By the curing means monomer is solidified, make substrate surface form coating, the Static Water contact angle of this coating surface is greater than 95 °.
Adopt ultrasonic ultrasonic delay line memory to make curable monomer produce the method for droplet, curable monomer is offered base material so that reduce the consumption of monomer.Droplet is discharged in the evaporation tube that is heated by band heater, and the droplet impact of atomizing is also flash evapn, i.e. flash distillation on the inwall of evaporation tube.Like this at monomer deposition before base material, the polymerization chance of monomer will reduce.
On the other hand, base material of the present invention can be a side waterproof, and can absorb and store the liquid of opposite side, or both sides all have water proofing property.
Detailed Description Of The Invention
The preferred embodiments of the invention will be described in detail belows, provide a kind of employing high-velocity electron beam method of radiating, in the method for the lasting waterproof coating of the surface coated of base material.Term " hydrophobic " and " waterproof " can be used with mutually, and the performance that lodges in this surperficial waterborne liquid (as body fluid) can be repelled in the surface that refers to material.Hydrophobicity and wettability can define by the Static Water contact angle, also can define by the surface tension of liquid and relevant solid.Related content has carried out at length discussing in " contact angle, wettability and tension force " american chemical society publication, that Robert F.Gould edits (publishing right 1964) book.If the Static Water contact angle is greater than 90 °, then the surface is hydrophobic, and liquid can not automatically spread on the surface of fabric.Generally speaking, the contact angle between surface and the liquid is big more, and the hydrophobicity on surface is strong more.
Coating of the present invention has " lasting hydrophobicity ", and after being exposed to liquid and humid air, the hydrophobic performance that base material is produced still keeps.
The thickness of coating that the inventive method forms preferably less than 2 microns, most preferably is the 0.001-1 micron less than 5 microns.This coating is to be formed by the curable monomer steam of vacuum deposit on removable base material, and base material is installed on the heated support thing of working continuously, and preferred cylinder is kept its temperature and is lower than and can evaporates the boiling point of monomer under the environment of vacuum storehouse.Owing to exist temperature difference, monomer vapor condensed is on the surface of base material.Be used for monomer material of the present invention and should have lower molecular weight,, be preferably 200-300AMU for 150-1000 atomic mass unit (AMU).The mixture of multi-functional fluorocarbon, particularly fluoro acrylic ester or simple function group fluoro acrylic ester and multi-functional fluoro acrylic ester are preferred.The monomer that is adopted or the mixture of monomer on average have about 2 or a plurality of pairs of keys (as a plurality of olefin groups), and the vapour pressure that is had can make it be condensate in the surface of base material.Can select such vapour pressure, for example vapour pressure is about 1.3310 under standard temperature and pressure (STP) -6Millibar-1.3310 -1Millibar is most preferably 1.3310 -2Millibar (promptly more lower boiling material).
The monomer of high vapour pressure is flashed at low temperatures, so heating process can not be degraded (cracking).Do not exist the content of unreacted degradation products or unreacted degradation products lower, can cause coating to have the volatile component content of reduction, deposited monomer all basically in the described coating are all reacted, and solidify to form complete film when contacting with radiation source.Although formed coating is very thin, because these characteristics, making to be coated with fully continuously becomes possibility.Film after the curing has good tack, and the chemical erosion of anti-organic solvent and inorganic salts.
Method of the present invention produces the substrate surface with hydrophobic property serially, and the Static Water contact angle that makes the surface is preferably greater than about 120 ° greater than 95 °, more preferably greater than about 130 °, and most preferably from about 150 °-Yue 165 °.Can adopt the water contact angle protractor to measure the Static Water contact angle.Mensuration should be carried out on smooth (being level) of base material after the coating and smooth surface.For the mensuration of water contact angle, " smooth " speech used herein is meant the roughness assay method by standard, and the roughness on continuous surface is not more than 5 microns.Curable fluorochemical monomer
According to the present invention, high-speed vacuum coating processing is carried out in the one or both sides of production water vapor permeable base material make it have excellent water resistance, need a kind of curable monomer component.This curable monomer of the obtained waterproof coating that meets the requirements contains fluorine-containing group.
In one embodiment of the invention, any suitable fluoromonomers all can use, including, but not limited to the copolymer of: fluoro acrylic ester monomer, fluoroolefin monomer, fluorostyrenic monomers, fluoro alkylene oxide monomer (as perfluoro propene oxid, perfluor epoxy hexane), fluorinated ethylene base alkyl ether monomer and they and suitable comonomer, wherein said comonomer is fluoro fluoro or non-.Preferably can carry out the fluoromonomers of polymerization by free radical polymerisation process.
In another embodiment of the invention, the monomer that is used for method of the present invention is fluorostyrenic monomers and fluorinated ethylene base alkyl ether monomer, and it is including, but not limited to alpha-fluoro ethene, β-fluorostyrene, α, β-difluoro-benzene ethene, β, β-difluoro-benzene ethene, α, β, β-trifluoro-benzene ethene, α-three fluoro methyl styrene, 2,4,6-three (three fluoro methyl) styrene, 2,3,4,5,6-phenyl-pentafluoride ethene, 2,3,4,5,6-five fluoro-α-Jia Jibenyixi and 2,3,4,5,6-five fluoro-betas-methyl styrene.
In another embodiment of the present invention, also tetrafluoroethylene can be used for method of the present invention, (for example: the copolymer of tetrafluoroethylene and perfluoro propyl vinyl ether), the copolymer and the perfluoro ionomer (as perfluorosulfonic acid ester ionomer, perfluoro carbonic acid ester ionomer) of tetrafluoroethylene-ethene including, but not limited to: the copolymer of hexafluoropropylene (HFP)/tetrafluoroethylene (TFE), the copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether.
In another embodiment of the invention, the fluorocarbon elastomer is that the fluorinated olefin polymer that a class can be used for the inventive method (is seen for example 7 Encyclopedia of Polymer Science ﹠amp; Engineering 257), its including, but not limited to: poly-(inclined to one side 1,1-difluoroethylene-hexafluoropropene) copolymer, poly-(inclined to one side 1,1-difluoroethylene-hexafluoropropene-tetrafluoroethylene) copolymer, poly-[inclined to one side 1,1-difluoroethylene-tetrafluoroethylene-perfluor (methyl vinyl ether)] copolymer, poly-[tetrafluoroethylene-perfluor (methyl vinyl ether)] copolymer, poly-(tetrafluoroethylene-propylene) copolymer, poly-(vinylidene fluoride-chloro trifluoro-ethylene partially) copolymer.
In a preferred embodiment of the invention, the performance of considering reactivity, the physical property of monomer component and adopting the cured film of this component formation, the fluoro acrylic ester class is specially adapted to as monomer material.Term used herein " fluoro acrylic ester monomer " is meant acrylic acid (H 2C=CHCOOH) or methacrylic acid (H 2C=CCH 3-COOH) ester class, ester group wherein is the group of a fluoro, as the alkyl of perfluoro.A used specific class fluoro acrylic ester monomer is as the represented compound of general formula (I) in the inventive method:
H 2C=CR 1-COO (CH 2) nR 2(I) wherein n is 1 or 2; R 1Be hydrogen or methyl; And R 2Be perfluoro aliphatic group or perfluoro aromatic group, for example perfluoro linearity or branching, saturated or unsaturated C 1-C 10Alkyl, phenyl or naphthyl.
In a specific embodiments of the present invention, R 2Be C 1-C 8Perfluoroalkyl or-CH 2-NR 3-SO 2-R 4, R wherein 3Be C 1-C 2Alkyl, R 4Be C 1-C 8Perfluoroalkyl.Term used herein " perfluoro " is meant that all or all basically hydrogen atoms are all replaced by fluorine on the organic group.Described monomer of above-mentioned general formula (I) and their abbreviation comprise following compounds:
Methacrylic acid 2-(N-ethyl PFO sulfonamido) ethyl ester (" EtFOSEA ");
Methacrylic acid 2-(N-ethyl PFO sulfonamido) ethyl ester (" EtFOSEMA ");
Acrylic acid 2-(N-methyl PFO sulfonamido) ethyl ester (" MeFOSEA ");
Methacrylic acid 2-(N-methyl PFO sulfonamido) ethyl ester (" MeFOSEMA ");
Acrylic acid 1,1-dihydro perfluor monooctyl ester (" FOA "); With
Methacrylic acid 1,1-dihydro perfluor monooctyl ester (" FOMA ").
In addition, curable monomer component can also comprise multi-functional acrylate, and this compounds is disclosed among the US 4842893, and its disclosure is incorporated herein by reference.Base material
According to method of the present invention, carry out substrates coated and can be the base material of any water vapor permeable.For example, this base material can be a porous membrane, and free air can be circulated by the hole, or woven fabric or nonwoven fabric, and free air also can circulate by the hole on woven fabric or the nonwoven fabric.Yet this base material also can not penetration air, for example microporous substrate (the being generally resilient calcium filling film) integral membrane that maybe can conduct steam.Particularly preferably be the aforesaid base material that can be used for clothes or adsorbable goods.Coating to base material can be carried out at one or both sides, and according to the required final use difference of this base material, coating can be identical or different.
Because the inventive method has ability low-cost and that can work continuously, so base material can be used in the disposable goods, as diaper, sanitary napkin, underpants, adult incontinence products, sweat pad under armpit, chest pad, shoe-pad or the like.Described base material has the sealing function of non-infiltration plate when being used for the either side of said products, therefore need this base material under the common user mode of goods, water vapor permeable, and liquid impermeable.On the other hand, this base material also can be used as the liquid-absorbent side that liquid infiltration base material is used for goods, the substrate surface deposited liquid can be transported in the absorbing structure by base material very soon, and this absorbing structure can not make the liquid reverse flow to the user of goods or (preventing to get wet once more) only just might take place under extreme condition.Can also be used for protective clothes by the inventive method substrates coated, as raincoat or gloves or cap or need the clothes of water vapor permeable.
Therefore, in view of so having described the present invention in detail, for a person skilled in the art, various variations within the scope of the present invention are conspicuous.Should not be considered as the present invention and only be confined to content described in the specification.

Claims (11)

1, a kind of method that adopts fluoromonomers coating water vapour permeable substrates, make the hydrophobic deg of this substrate surface reach the contact angle of Static Water greater than 95 °, and keep the water vapour permeability of described base material, described method is carried out in the vacuum storehouse, this vacuum storehouse is contained: (i) supporter that moves to second position from first position, (ii) evaporimeter that import and steam (vapor) outlet are housed, when above support is on described first position, the contiguous above support of described outlet, (iii) on second downstream position of above support, exist equipment that is cured and the temperature of (iv) keeping above support to be lower than the equipment of described evaporator temperature; Said method comprising the steps of:
(a) described base material is placed on the described mobile heated support thing, and make the surface of described base material sequentially pass through described steam (vapor) outlet and described curing apparatus;
(b) temperature of keeping described base material is lower than the evaporating temperature of described fluoromonomers;
(c) gas in the discharge vacuum storehouse makes the pressure in the described storehouse be lower than 1.35 MPas;
(d) select a kind of curable fluoromonomers component, its mean molecule quantity is the 150-1000 atomic mass unit, and the vapour pressure that has makes its condensation under the described temperature and pressure of described substrate surface;
(e) a certain amount of described curable components of metering feeds the described import of described evaporimeter;
(f) in described evaporimeter, evaporate described curable component, and discharge the curable components of having evaporated by the outlet of described evaporimeter;
(g) above support that will be loaded with described base material moves to second position with the speed greater than 1 cel from described first position, makes the substrate passed described vapor outlet port and described curing apparatus;
(h) make described monomer component on the described substrate surface be condensed to thickness less than 5 microns film; Move described the substrate passed described vapor outlet port simultaneously.
(i) when moving described the substrate passed described curing apparatus, the monomer film of described condensation carries out crosslinked, preferably runs through the described thickness of described film.
2, method according to claim 1, the water contact angle on treated surface are preferably greater than 130 ° greater than 120 °, most preferably are 150 °-165 °.
3,, it is characterized in that described base material is fluoridized film or fibre fabric or fabric nonwoven cloth according to the method for aforementioned arbitrary claim.
4, according to the method for aforementioned arbitrary claim, the mean molecule quantity that it is characterized in that described curable components is the 200-300 atomic mass unit.
5, according to the method for aforementioned arbitrary claim, the described translational speed that it is characterized in that above support is 2 meter per seconds-40 meter per seconds, is preferably 5 meter per seconds-20 meter per second.
6, according to the method for aforementioned arbitrary claim, the thickness that it is characterized in that described monomer component film is preferably 0.001 micron-1 micron less than micron.
7, according to the method for aforementioned arbitrary claim, the temperature maintenance that it is characterized in that described shiftable support is at 20 ℃-80 ℃.
8,, it is characterized in that comprising in the described evaporimeter flashing apparatus of described curable components according to the method for aforementioned arbitrary claim.
9,, it is characterized in that described shiftable support comprises a cylinder according to the method for aforementioned arbitrary claim.
10,, it is characterized in that described curing apparatus contains the gas discharge electron beam according to the method for aforementioned arbitrary claim.
11, according to the method for aforementioned arbitrary claim, it is characterized in that also being included in this method the step that described step (h) activates the surface of described goods before, its using plasma is handled described substrate surface, the plasma of preferred molecular oxygen or argon.
CN99816892.0A 1999-09-07 1999-09-07 Process for hydrophobic treatment of water vapour permeable substrates Pending CN1367721A (en)

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MXPA02002451A (en) 2002-07-30
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