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.
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.