CN101892585A - Method for manufacturing hydrophilic fiber article - Google Patents
Method for manufacturing hydrophilic fiber article Download PDFInfo
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- CN101892585A CN101892585A CN2009102029662A CN200910202966A CN101892585A CN 101892585 A CN101892585 A CN 101892585A CN 2009102029662 A CN2009102029662 A CN 2009102029662A CN 200910202966 A CN200910202966 A CN 200910202966A CN 101892585 A CN101892585 A CN 101892585A
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Abstract
The invention discloses a method for providing a durable hydrophilic coating for a substrate. The method comprises the following steps of: making thermoplastic fibers contacted with a coating combination of aqueous dispersion containing silicon diode nano particles with an average particle size of 100 nanometers or less than 100 nanometers, wherein the pH value of the aqueous dispersion of the silicon diode nano particles is less than about 3; and drying the thermoplastic fibers and the coating combination to form a silicon diode nano particle coating. The silicon diode nano particles can further contain hydrophilic surface modified groups.
Description
Technical field
This specification relates to the fiber article with nanoparticle coating, and more particularly, relates to the floor file object with nanoparticle coating, and to the method for fiber article coated nanoparticles coating.
Background technology
In many application, wish the object on possess hydrophilic property or water wettability surface.For instance, in the environment that rains, the water droplet that the water in ground cushion enters building with fast Absorption people's the shoes need be provided on the building doorway or shake the water droplet that falls or drip from the people's that enters building coat from umbrella.In some places, usually use cotton system doormat, it can absorb water fast but persistence is bad, and is often mouldy and therefore need to change doormat.The doormat of other type can be by making such as artificial fibres such as nylon or polypropylene, and it may be difficult for mildew, but these materials may not absorb water very apace.
The known hydrophilic coating of fibrous material comprises the coating described in the following document: United States Patent (USP) the 6th, 136, No. 215 (siloxane treated of textiles (siloxane treatments for textiles)), United States Patent (USP) the 6th, 436, No. 855 (fibre finish (fiber finishing prior to high speed manufacture of water-absorbing articles) before the High-speed machining suction object) and WO2003097925 (with the polymer treatment synthetic fiber (treatment of synthetic fibers with polymers that contain carboxyl groups) that contain carboxyl).
United States Patent (USP) the 7th, 112 has been described in No. 621 and has been used the functionalized pressure release surface of nanoparticle systems.
For example, as United States Patent (USP) the 5th, 585, No. 186, the 5th, 723, No. 175, the 5th, 753, No. 373 and the 6th, 040, the hydrophily character of using Nano particles of silicon dioxide that antifog application is provided has been described among No. 053 and the US20040237833.
United States Patent (USP) the 5th, 908, No. 663, the 7th, 407, No. 899 and the 7th, 485, a part of using nano particle to handle as carpet surface has been described in No. 588, wherein handling provides liquid-repellant and stain resistance usually.
Summary of the invention
In certain embodiments, a kind of method of making the fiber article of permanent hydrophilic is described, described method comprises that to make thermoplastic fibre be that the coating composition of the aqueous liquid dispersion of the following Nano particles of silicon dioxide of 100 nanometers or 100 nanometers contacts with comprising average grain diameter, the pH value of the aqueous liquid dispersion of wherein said Nano particles of silicon dioxide is less than about 3 and dry so that the Nano particles of silicon dioxide coating to be provided.
In some embodiment of described method, the concentration of Nano particles of silicon dioxide is that 5wt% is to 20wt% in the coating composition.
In some embodiment of described method, thermoplastic fibre was hydrophobicity before handling through Nano particles of silicon dioxide.
In some embodiment of described method, thermoplastic fibre comprises the thermoplastic resin that is selected from by polyamide, polyester, polypropylene, polyurethane, polyvinyl chloride, its blend and the group that forms.
In some embodiment of described method, the average grain diameter of Nano particles of silicon dioxide is about 20 nanometers or below 20 nanometers.
In some embodiment of described method, the average grain diameter of Nano particles of silicon dioxide is about 10 nanometers or below 10 nanometers.
In some embodiment of described method, Nano particles of silicon dioxide comprises the surface modification Nano particles of silicon dioxide.Described surface modification Nano particles of silicon dioxide can comprise the surface modifier with following chemical formula:
[(Z)
c-R
3]
d-Si-(OR
4)
b(R
4)
4-(b+d)，
Wherein
Z is a hydrophilic radical;
R
3For covalent bond or randomly replaced by at least one oxygen atom and randomly by-divalence with about 1 to 20 carbon atom or trivalent hydrocarbon bridge linkage group that the OH base replaces;
R
4Be hydrogen or alkyl, the aryl or aralkyl that randomly replace independently with 1 to 8 carbon atom through oxygen, nitrogen and/or sulphur atom;
C is 1 or 2, b be 1 to 3 and d be 1 or 2 and (b+d)≤4.
In some embodiment of described method, the group that the optional free carboxylic acid group of Z, sulfonic group, phosphonate group and its salt are formed.
In some embodiment of described method, the group that optional free hydroxyl alkyl of Z and poly-hydroxyalkyl are formed.
In some embodiment of described method, the group that optional free oxidation thiazolinyl of Z and polyoxyalkylenes are formed.
In some embodiment of described method, Z can comprise quaternary ammonium group.
In some embodiment of described method, it is 100nm or the Nano particles of silicon dioxide below the 100nm that the coating composition of described method comprises the average grain diameter of 80wt% to the water of 95wt% and 5wt% to 20wt%, and wherein the pH value of coating composition is less than about 3.
In above any embodiment of described method, coating composition all can have the pH value less than about 2.
In certain embodiments, describe a kind of hydrophily object, wherein said hydrophily object is prepared by aforementioned arbitrary embodiment of described method.
In certain embodiments, measured as absorbing test (Water Droplet Absorption Test) at least 10 washing circulation backs of carrying out according to washing test (Laundering Test) according to water droplet, the hydrophily object has less than about 10 seconds MAT.The details that water droplet absorbs test and washing test are described in the example chapters and sections.
In certain embodiments, measured as absorbing test at least 10 washing circulation backs of carrying out according to the washing test according to water droplet, the hydrophily object has less than about 5 seconds MAT.
In certain embodiments, measured as absorbing test at least 20 washing circulation backs of carrying out according to the washing test according to water droplet, the hydrophily object has less than about 5 seconds MAT.
In certain embodiments, the hydrophily object is a ground cushion.
Description of drawings
Do not have
The specific embodiment
For following defined term,, otherwise should use these definition unless other place provides different definition in claims or this specification.
Term " polymer " " should understand comprise polymer, copolymer (for example, the polymer that utilizes two or more different monomers to form), oligomer and its combination and can be for example by co-extrusion or the reaction that comprises ester exchange polymer, oligomer or copolymer can miscible blend to form.Unless otherwise mentioned, otherwise in block copolymer and random copolymer be also included within.
Term " nano particle " defines in this article and means the particle of diameter less than about 100nm.
Term " surface-modified nanoparticles " is meant and comprises chemical group or the particle partly that for example is connected with particle surface by covalent bond.Surface group changes the physics or the chemical characteristic of particle.
The wetting fiber or the fiber surface of aqueous fluids (for example water droplet) that can be dropped on it described in term " hydrophilic " as used herein.The hydrophily of fiber be with respect in the example in greater detail water droplet absorb test and define, and average water droplet soak time is considered as hydrophily less than about 10 seconds fiber article.
As the term " permanent hydrophilic " that is used for the fiber article of this specification be meant according to washing test (describing herein) such as 2 circulations, more than 5 times, more than 10 times, more than 15 times or more than 20 times or more times wash cycle etc. repeatedly after the wash cycle, keep less than about 10 seconds (such as absorb by water droplet test mensuration) average water droplet soak time.
Enumerate number range by end points and comprise all numerical value (for example 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) that comprise in the described scope.
Such as in this specification and the appending claims use, unless offer some clarification in addition, otherwise singulative " " and " described " comprise a plurality of indicants.Therefore, for example mention that the composition that contains " compound " comprises the mixture of two or more compound.Such as in this specification and the appending claims use, unless offer some clarification in addition, otherwise term " or " usually with it comprise " and/or " implication use.
Unless otherwise mentioned, otherwise in this specification and claims employed all be expressed as the numerical value that dosis refracta, character measure etc. and all be interpreted as in all cases being modified by term " about ".Therefore, unless do opposite explanation, otherwise the approximation that the numerical parameter of being set forth in aforementioned specification and the appending claims is a desirable properties that visual those skilled in the art utilizes teaching of the present invention to reach out for to be changed.Do not plan to limit the application of doctrine of equivalents for the scope of claims, each numerical parameter at least should be according to the number of the significant digits of being reported and by using the technical interpretation that generally rounds off at all.Although setting forth the number range and the parameter of broad range of the present invention is approximation, as far as possible accurately report the numerical value described in the particular instance.Yet any numerical value all contains some inevitable error inherently, and this is produced by visible standard deviation in its corresponding thermometrically.
Comprise described hydrophilic fibre herein such as objects such as ground cushions when after at least 10 wash cycle of carrying out, absorbing when testing according to water droplet according to the washing test, can represent less than about 10 seconds durable hydrophilic property.In a preferred embodiment, MAT was less than 5 seconds, 4 seconds, 3 seconds, 2 seconds or 1 second.
What describe at present is the method for making hydrophilic fiber article, described method comprises makes polymer fiber contact with the aqueous liquid dispersion of hydrophily Nano particles of silicon dioxide, wherein said Nano particles of silicon dioxide randomly comprise the surface modification Nano particles of silicon dioxide and wherein the gained coating make described polymer fiber become hydrophilic.
Hydrophily
The hydrophily of fiber or shortage hydrophily can stand water droplet absorption test as described below by the appropriate samples that makes this fiber and determine.For for simplicity, fiber sample is defined as to have and equals to absorb 1 " the water droplet soak time " that drips (about 0.2mL) required time.Have＞fiber sample of 90 seconds water droplet soak time can be considered and have bad hydrophily, and the hydrophily that the water droplet soak time indicating fiber sample of 10 seconds or 5 seconds, 4 seconds, 3 seconds, 2 seconds or 1 second is become better and better.
The hydrophilic persistence of fiber or lack persistence and can stand to repeat the washing circulation, then make fiber sample stand water droplet to absorb test and determine by making fiber sample according to what the washing test of describing in the example chapters and sections was carried out.Only after 5 washing circulations carrying out according to washing test, just showing that the fiber sample that hydrophily reduces can have bad persistence, and 10 times, 15 times that carry out according to the washing test or even 20 washing circulations after still keep hydrophilic fiber sample can have good hydrophilic persistence.
The fiber article substrate
The polymer fiber substrate of this disclosure can have any known structure, comprises knitted construction, knitting structure, non-knitting structure etc. or its combination.The polymer fiber substrate can have the weight between every square yard about 1 ounce and about 55 ounces.Can preferably have weight between every square yard about 20 ounces and about 50 ounces such as polymer fiber substrates such as floor file objects.
In this disclosure, suitable polymer fiber substrate can comprise the mat of ground cushion, cloth, rag (wiping sheet) or various other types.The polymer fiber of this disclosure is contained any standard fibers and its composite that uses in the floor file object.Polymer fiber can comprise carpet surface (carpet face) the form existence that monfil, core-sheath-type fiber etc. maybe can enclose suede, clipping or any other type.Only for instance, fiber cluster ground such as nylon, polyethylene, polypropylene, polyester, polyvinyl chloride, polyurethane run through fabric (such as the braiding of any fiber type, non-braiding or knit goods, such as previous listed fabric).
The polymer fiber substrate can comprise the fiber or the yarn of virtually any size, comprises that little dawn counts fiber or yarn (fiber or the yarn of filament denier (denier per filament) less than 1).Described fiber or yarn can have less than about 0.1 filament denier to about 2000 filament deniers or be more preferably less than the dawn number of about 1 filament denier in about 500 filament denier scopes.
In certain embodiments, untreated polymer fiber substrate comprises and has bad hydrophily the ground cushion of (just, have＞90 seconds water droplet soak time).In certain embodiments, the polymer fiber substrate can comprise ground cushion, wherein fiber can be as United States Patent (USP) the 4th, 820, described in No. 566 (extra large alunite people such as (Heine)) and the United States Patent (USP) the 5th, 055, No. 333 (extra large alunite people such as (Heine)), be the tufting cast formula of inserting in the back lining materials, described two pieces of patents all are incorporated herein by reference.In certain embodiments, ground cushion can comprise such as can available from 3M company (Sao Paulo, the Minnesota State (and St.Paul, MN) and commercially available doormats such as the NOMAD 4000 of Chinese Shanghai (Shanghai, China)), NOMAD 5000 and NOMAD 6000.
In certain embodiments, except that the polymer fiber of this specification, fiber article can comprise natural fabric in addition or be derived from the fiber of natural fabric, comprises silk, wool and cotton fiber, or cellulose acetate fibre and associated fiber or its combination.Yet this specification is usually at the fiber article that comprises polymer fiber as described below.
Polymer fiber
The permanent hydrophilic fiber can be by representing＞the fluoropolymer resin preparation of hydrophobic usually (for example, the thermoplasticity or the thermosetting) of 90 seconds water droplet soak time.Suitable thermoplastic polymer can comprise such as commercial polymers (commodity polymer) such as poly-(vinyl chloride), polyethylene (high density, low-density, extra-low density), polypropylene; Such as polyester (for example comprising poly-(Polyethyleneglycol Terephthalate) and poly-(butylene terephthalate)), polyurethane and polyamide engineering plastics such as (for example comprising nylon); Blend and mixture with these materials.
On the one hand, hydrophilic fiber article comprises the substrate that is selected from by extruded material, melt-blown material, braided fabric, non-woven fabric, foaming body and its group that forms.
Object comprises the polymer fiber substrate with coating.In certain embodiments, coating comprises the Nano particles of silicon dioxide component, wherein Nano particles of silicon dioxide long time without surface modification agent still modification.The existence of these " unmodified " or " naked " Nano particles of silicon dioxide can make the surface of polymer fiber become hydrophilic on the polymer fiber, especially when Nano particles of silicon dioxide be when the pH value applies less than about 3 aqueous solution.
In certain embodiments, coating comprises the surface modification Nano particles of silicon dioxide component that has surface modifier on the surface.Containing surface-modifying groups can make fiber surface become hydrophilic as the existence of the coating of hydrophilizing agent.More particularly, surface-modifying groups is to be enough to form individual layer or covalently bound less than the amount and the nanoparticle surface that cover individual layer.May wish not exclusively modification of available surface functional group (just, silanol), associate via unmodified silanol surface group and the substrate of remnants to allow nano particle.
Other fibrous substrate
In some respects, fibrous substrate can comprise natural fabric and the fiber that is derived from natural fabric.Measured as absorbing test by water droplet, these fibers may have hydrophily to a certain degree.
In some respects, fibrous substrate can comprise the combination of cellulose acetate, natural silk, wool, cotton and these fibers.
We think that the naked Nano particles of silicon dioxide coating of the surface modification Nano particles of silicon dioxide of this specification and acidifying can be coated on these fibers and as to absorb test by water droplet measured, make hydrophilicity increase.May need the pH value of coating composition is adjusted in the scope of not destroying these fibers.For instance, may need the pH value is adjusted to about 3 in about 5 scope.
Nano particle
Nano particle is the inorganic nano-particle that has surface-modifying groups on the surface.Suitable inorganic nano-particle comprises Nano particles of silicon dioxide.Nano particles of silicon dioxide uses with the dispersion of submicron-scale Nano particles of silicon dioxide in aqueous solvent or aqueous organic solvent mixture usually.The average grain diameter of Nano particles of silicon dioxide can be 100 nanometers or below 100 nanometers, preferred 30 nanometers or below 30 nanometers, and more preferably 10 nanometers or below 10 nanometers.Average grain diameter can be greater than about 2 nanometers.Particle mean size can be utilized determination of transmission electron microscopy.In case of necessity, the big silicon dioxide granule of at least a portion can be present in the coating composition, and its amount does not reduce the hydrophily of selected substrate.Nano particle can be the colloidal dispersions form.
In certain embodiments, surface-modified nanoparticles can provide improved dispersion stability.Under the situation of bound by theory not, according to the character and the molecular dimension of surface modifier, surface modification can increase space and/or the electrostatic stabilization effect between the particle, thereby stops it to be combined together to form bigger unstable aggregation.Under described situation, the use of surface-modified nanoparticles can act synergistically with lower pH value of solution value, more stable dispersion composite is provided or enlarges to disperse composite stable p H value scope.This can allow to use product under almost neutral pH value level, thereby can reduce the user is produced the possibility that stimulates or endanger.
Know in the affiliated field of inorganic silicon dioxide nano particle (colloidal sol) in the aqueous medium, and can buy from market.Silicon dioxide gel in water or alcohol solution can be such as LUDOX (by (the E.I.du Pont de Nemours and Co. of E.I.Du Pont Company of Wilmington,State of Delaware, US, Inc., Wilmington, Del., USA) manufacturing), NYACOL is (from Massachusetts ashland Buddhist nun's subfamily that (the Nyacol Co. of company, Ashland, MA) obtain) or NALCO (by (the Nalco Chemical Co. of Nalco Chemical Co of Illinois, USA Naperville, Naperville Ill.USA) makes) etc. brand name buy.A kind of suitable silicon dioxide gel is NALCO 2326, and it is the silicon dioxide gel of particle mean size 5 nanometers, pH value 10.5 and solids content 15 weight %.Other Nano particles of silicon dioxide that can buy comprise can available from Nalco Chemical Co " NALCO 1030
TM", " NALCO 1034A
TM", " NALCO1050
TM", " NALCO 1115
TM", " NALCO 2326
TM", " NALCO 2327
TM", " NALCO2329
TM" and " NALCO 1130
TM"; Can be available from Rui Maite company (Remet Corp.) (New York, United States Utica (Utica, NY, USA)) " Remasol SP30 "; With can be available from " the LUDOX SM " of E.I.Du Pont Company.
Also can use the non-aqueous colloidal sol of silica (being also referred to as the silica organosol), it is the silicon dioxide gel dispersion liquid of organic solvent or aqueous organic solvent for liquid phase.In enforcement of the present invention, silicon dioxide gel is through selecting so that its liquid phase and aqueous solvent or aqueous organic solvent are compatible.Yet, observed before using such as organic solvent dilutings such as ethanol, at first should make the acidifying of stable sodium Nano particles of silicon dioxide.Dilute before the acidifying and may produce bad or uneven coating.Ammonium stabilized chlorine silicon nano usually can any serial dilution and acidifying.
Surface modifier
Several different methods can be used for the surface of modified Nano particle, for example comprises to nano particle (for example powder or colloidal dispersions form) adding surface modifier and making surface modifier and the nano particle reaction.Other useful surface-modifying is handled and for example is described in United States Patent (USP) the 2nd, 801, No. 185 (Yi Le (Iler)) and the United States Patent (USP) the 4th, 522, No. 958 (Da Si people such as (Das)).Surface-modifying groups can surface-derived modifier.Surface modifier can be by chemical formula R
S-R
L-Z schematically shows, wherein R
SBe the surface bound groups that can connect, Z with the silanol (just, the Si-OH group) on the silica particle surface represent not with system's (for example, substrate) in the hydrophilic radical of other component reaction, and R
LRepresent organic linking group or key.The suitable surface bound groups R of surface modifier
SCan comprise silanol, alkoxy silane or chlorosilane.In certain embodiments, hydrophilic radical Z can be non-alkaline hydrophilic radical, such as acidic group (comprising carboxylic acid group, sulfonic group, phosphonate group, its salt or its combination), ammonium or poly-(ethylene oxide) base or hydroxyl.
The consumption of described surface modifier can make 5% to 100% surface silanol groups (Si-OH group) of Nano particles of silicon dioxide functionalized.Usually make at least 60%, 70%, 80% or 90% functionalisation of surfaces of Nano particles of silicon dioxide.When drying, the residual surface silanol is applicable to producing the Nano particles of silicon dioxide WEB.Be determined by experiment the number of functional group, wherein make the reaction of a large amount of nano particles and excessive surface modifier so that all available reactive moieties are all functionalized by surface modifier.Can calculate lower functionalized percentage by the result then.The consumption of surface modifier is enough to provide surface modifier with respect to more than the twice as high molar ratio of the surface silanol groups on the inorganic nano-particle usually.Excessive alkoxy silane can be used for producing the above functionalized Nano particles of silicon dioxide of one deck, and can be used for forming between particle when dry coating siloxanes chemistry key.For on Nano particles of silicon dioxide, obtaining the surface modifier of preferred high concentration, importantly at first make the Nano particles of silicon dioxide surface modification, afterwards with the remaining combination of components of coating.
In certain embodiments, surface modifier has following chemical formula:
[(Z)
c-R
3]
d-Si-(OR
4)
b(R
4)
4-(b+d)，
Wherein
Z is a hydrophilic radical;
R
3For covalent bond or randomly replaced by at least one oxygen atom and randomly by-divalence with about 1 to 20 carbon atom or trivalent hydrocarbon bridge linkage group that the OH base replaces;
R
4Independently for hydrogen or randomly at alkyl, the aryl or aralkyl with 1 to 8 carbon atom that can utilize the position to replace through oxygen, nitrogen and/or sulphur atom;
C is 1 or 2, b be 1 to 3 and d be 1 or 2 and (b+d)≤4.
In certain embodiments, Z is the hydrophilic radical that is selected from the group that is made up of carboxylic acid group, sulfonic group, phosphonate group and its salt.The example of useful surface-modifying agent comprises following each thing:
(HO)
3SiCH
2CH
2CH
2SO
3H，
(HO)
3SiCH
2CH
2CH
2OCH
2CH(OH)CH
2SO
3H，
NaOSi(OH)
2CH
2CH
2CH
2SO
3Na，
NaOSi(OH)
2CH
2CH
2CH
2OCH
2CH(OH)CH
2SO
3Na，
NaOSi (OH)
2CH
2CH
2CO
2Na and
NaOSi(OH)
2CH
2CH
2P(O)(OH)
2ONa
And other known compound.The sulfonate organic silane compound can be according to United States Patent (USP) the 4th, 338, the program preparation seen in No. 377 (Bake people such as (Beck)).Containing the carboxyl surface-modifying groups such as carboxyethyl silantriol sodium salt etc. can be available from the lid (Mo Liweier of Pennsyivania (Morrisville, PA)) of Leicester company (Gelest).
In another embodiment, surface modifier can comprise a hydrophilic ether, and it can comprise oxyalkylene or polyoxyalkylene, comprises for example polyoxyethylene ene compound.The example of a useful surface-modifying agent be can available from the lid Leicester company (Mo Liweier of Pennsyivania) 2-[methoxyl group (polyethylene glycol oxide) propyl group] trimethoxy silane.
In another embodiment, for example can comprise can be available from the sugared silane of N-(the silica-based propyl group of the 3-triethoxy) glucamide of lid Leicester company (Mo Liweier of Pennsyivania) for surface modifier.
In another embodiment, surface modifier can comprise quaternary ammonium group.The non-limiting example that comprises the surface modifier of ammonium is the (Gelest of lid Leicester company available from the Mo Liweier of Pennsyivania, Inc., Morrisville, PA) the silica-based propyl group-N of trimethoxy, N, N-trimethyl ammonium chloride (TTMS, 50% in methyl alcohol) and N-(the silica-based propyl group of trimethoxy) ethylenediamine triacetic acid (EDTAS).
In another embodiment, surface modifier can comprise such as epoxy radicals alkoxy silane grafting groups such as (for example 3-glycidoxypropyl triethoxysilanes) (grafting group) or such as michael acceptor group (Michael acceptor group) such as acrylate-based.The example that contains acrylate-based surface modifier is can be available from the methacryloxypropyl trimethoxy silane of General Corporation (GECompany).
In another embodiment, surface modifier can comprise the aromatic sulfonyl silane compound, for example can be available from 2-(the 4-chlorosulfonyl phenyl) ethyl-trimethoxy silane of lid Leicester company (Mo Liweier of Pennsyivania).Though be not bound by any theory, think sulfonic acid chloride group (SO
2Cl) can comprise that hydrolysis forms sulfonic group (SO under the surface modification condition of water
3H).
In another embodiment, surface modification hydrophilic nano particle can randomly make up with naked Nano particles of silicon dioxide, and wherein naked Nano particles of silicon dioxide is preferably through the inorganic acid acidifying.We find that these naked Nano particles of silicon dioxide are applicable to generation durable hydrophilic property coating when making up with above-mentioned surface modification Nano particles of silicon dioxide.Naked Nano particles of silicon dioxide can produce manufacturing cost than the low durable hydrophilic property coating of coating that mainly comprises the surface modification Nano particles of silicon dioxide with these combinations of surface modification Nano particles of silicon dioxide.
In certain embodiments, surface-modified nanoparticles can carry out drying and easily be scattered in the solvent of coating composition.
Liquid carrier
Described coating composition comprises liquid carrier.In a preferred embodiment, liquid carrier comprises water.Though coating composition does not require organic solvent, can contain water-soluble or the water miscibility organic solvent.Total VOC content of composition should preferably less than about 15wt%, and be more preferably less than about 10wt% less than about 20wt% of composite gross weight.Water-soluble or water miscibility organic solvent is preferably low-molecular-weight alcohol, preferably have carbon number, comprise butanols, isopropyl alcohol, ethanol and/or methyl alcohol and these alcohol mixture to each other or the mixture of these alcohol and the water-soluble or water miscibility organic solvent of VOC free less than about 6.The ability of using a small amount of described solvent (consumption meets existing U.S. EPA rules (for example referring to EPA 40C.F.R.51.100 (s) and case continuously)) to help to reduce wetting on hydrophobic surface of the surface tension of coating composite and these composites of improvement and sprawl.In addition, alcoholic solvent especially can be by participating in giving additional storage stability with the balance condensation reaction of alkoxy silane.
The pH value
Before coating on the fiber, available pKa (H
2O)＜5, preferably less than 2.5, most preferably the aqueous liquid dispersion of Nano particles of silicon dioxide (no matter naked Nano particles of silicon dioxide, surface modification Nano particles of silicon dioxide still be its combination) is acidified to the pH value level of expectation less than 1 acid.The acid that is suitable for comprises organic acid and inorganic acid and can be for example ethanedioic acid, citric acid, benzoic acid, acetate, formic acid, propionic acid, benzene sulfonic acid, H
2SO
3, H
3PO
4, CF
3CO
2H, HCl, HBr, HI, HBrO
3, HNO
3, HClO
4, H
2SO
4, CH
3SO
3H, CF
3SO
3H, CF
3CO
2H and CH
3OSO
2OH.Most preferred acid comprises HCl, HNO
3, H
2SO
4And H
3PO
4In certain embodiments, be desirable to provide the mixture of organic acid and inorganic acid.In certain embodiments, can use the acid that comprises pKa≤5 (preferred＜2.5, most preferably less than 1) and other sour acid blend of a small amount of pKa＞5.Found to utilize the weaker acid of pKa 〉=5 that the uniform coating that has such as desirable propertieses such as cleanablity and/or persistence can not be provided.Specifically, comprise the coating composition of weaker acid or alkaline coating composition and on the surface of polymeric substrate, form the liquid pearl usually.
In most of embodiment, coating composition contain usually enough acid with provide less than 5, preferably less than 4, be more preferably less than 3 and most preferably less than about 2 pH value.In certain embodiments, as if absorb the water droplet soak time that still has in the test less than 10 seconds or 5 seconds, 4 seconds, 3 seconds, 2 seconds or 1 second for the persistence that obtains to stand washing more than 10 times or 10 times in the washing test and at water droplet, making the pH value of coating composition is keys less than about 2.
Other additive
Described fiber and method can further comprise other optional component in coating.For instance, adding the wetting agent that is generally surfactant may be useful.Term " surfactant " is described in the molecule that comprises hydrophily (polarity) district and hydrophobicity (nonpolar) district on a part as used herein, and its size is enough to reduce the surface tension of coating solution.Can comprise that suitable surfactant is to help surface modifier at the lip-deep wettability of Nano particles of silicon dioxide.The example of suitable surfactant is for known to the one of ordinary skill in the art and can comprise for example poly-silica surfactant of nonionic.
Coating process
Can carry out the surface of substrate before applying coating prepares.The ability that the performance of coating can significantly be subjected to suitably to adhere on the base material influences.The existence meeting of surface contaminant, oil, grease and oxide weakens and reduces coating physically in suprabasil adherence.But surface treatment or clean substrate are to improve coating in suprabasil adherence.
In an embodiment of this disclosure, but the substrate of surface treatment ground cushion.The surface-treated method comprises vacuum moulding machine, corona, laser, chemistry, heat, flame, plasma, ozone and its combination.One or more these surface treatments may must be carried out when accepting the nanoparticle coating of this specification preparing non-polar fibers.
On the one hand, this specification comprises the hydrophilic fiber article that utilizes the method generation that comprises following steps: with the coating solution coating polymer fiber of the aqueous liquid dispersion that comprises the hydrophily Nano particles of silicon dioxide, wherein said hydrophily Nano particles of silicon dioxide can be surface modification Nano particles of silicon dioxide, naked Nano particles of silicon dioxide or its combination.
Coating process generally includes the polymer fiber with over coating solution coat object, comprises optional heating, drying and/or washing step.Though having found in some cases may be at least about 0.42g/m
2The surface modification Nano particles of silicon dioxide realize the durable hydrophilic property of this specification, but wish by utilizing excessive coating solution that higher coating level is provided.
In certain embodiments, coating process can comprise applying coating material, makes coating air-dry at ambient temperature then.In other embodiments, coating process can comprise heating to quicken coating process easily.In certain embodiments, coating process can comprise coating material is coated in the substrate, is in 90 ℃ to the 120 ℃ environment in the scope in temperature then and heats substrate.Heating-up temperature is preferably through selecting not cause the substrate degraded.Under the situation that does not have heating, be about 20-24 hour typical drying time; If the substrate that heating was coated with in 90 ℃ to 120 ℃ scope can shorten to about 1 hour drying time or even about 30 minutes so.
In certain embodiments, the method for coating Nano particles of silicon dioxide can further be included in the dry rinsing step of flush away over coating material afterwards in substrate.In a preferred embodiment, flushing liquid is a water.
The coating of this disclosure can be coated in the selected substrate by various coating techniques, other coating technique that described technology comprises that dip-coating, spraying, foaming coating, roller coat (roller), roll are coated with that (nip roller), flexible roll are coated with (flexible nip roller), pad coating (pad coating), know in overflow coating (flood coating) and the affiliated field.
The water-wash resistance test
Concerning the fiber that some were coated with, the maintenance water-wet behavior may be very important after repeatedly washing circulates.We make the permanent hydrophilic coating that washes with water on test (hereinafter described) the assessment fiber.We use Whirlpool (Whirlpool) 111 roof-mounted washing machines to carry out method of testing in test model.Think that this method of testing can be applicable to the washing machine of other model.
The coating composition of this disclosure of more detailed description and through the coating object in the following example, these examples are planned only as an illustration, because concerning the those skilled in the art, many modifications and variations within the scope of the present invention will be conspicuous.Unless otherwise mentioned, otherwise all umbers, percentage and the ratio reported in the following example are all by weight, and employed all reagent all derive from or can be available from chemical supplier hereinafter described in the example, or can be synthetic by routine techniques.
Example
Material
The Nano particles of silicon dioxide dispersion liquid can Nalco 2326
TM(particle mean size is 5nm), Nalco 2327
TM(20nm) with Nalco 2329
TM(75nm) with Nalco 1034A
TM(particle mean size is 20nm) is available from the Nalco Chemical Co of Illinois Naperville.
Nomad
TM6000 ground cushions: the nylon fiber ground cushion, can be available from the 3M (China) of Chinese Shanghai.
2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group] propane-1-sulfonic acid, according to United States Patent (USP) the 4th, 338, the program preparation in No. 377.
A-174: methacryloxypropyl trimethoxy silane, General Corporation.
SIM6492.7:2-[methoxyl group (polyethylene glycol oxide) propyl group] trimethoxy silane (MW=450-600), the lid Leicester company on Mo Liweierdong steel road, Pennsyivania No. 11 [19067] (Gelest, Inc., 11 East Steel Road, Morrisville, PA 19067).
The carboxyethyl silantriol sodium salt of SIC2263.0:25% in water, the lid Leicester company on Mo Liweierdong steel road, Pennsyivania No. 11 [19067].
2-(the 4-chlorosulfonyl phenyl) ethyl trimethoxy silane of SIC2417.0:50% in carrene, the lid Leicester company on Mo Liweierdong steel road, Pennsyivania No. 11 [19067].
The KH560:(3-glycidoxypropyl) trimethoxy silane, and the Zhejiang chemical science and technology group in Chinese Hangzhou (Zhejiang Chem-Tech Group Co., Ltd., Hangzhou, China).
Specimen
Unless otherwise mentioned, otherwise the specimen of the ground cushion of specified type cuts into the square that is of a size of 5cm * 5cm.
The washing test
Make the specimen that was coated with in the roof-mounted washing machine of standard, stand to repeat the washing test.With sample and ballast load (90 * 90cm flanging cloth of not putting the plain cloth fabric in order of about 250 gram/rice, cotton or 50/50 cotton/polyester) is placed in the washing machine, produce the gross weight of 1.8 ± 0.2kg (4 ± 0.5 pounds), wherein the pressur loading weight load is no less than 1.4kg (3 pounds).Add liquid detergent (the antifouling concentrated shampoo of 75g 3M carpet (Soil Retarding Carpet Shampoo concentrate), can be available from Sao Paulo, Minnesota State 3M company), and reach the peak level mark to the washing machine water filling, water temperature is 41 ± 3 ℃ of degree.With " standard " washing and dewatering cycle washing sample 45 minutes, totally 5 wash cycle, then under 40 ℃ in forced ventilation circulation baking oven dry specimen spend the night.The tester can randomly change the number of times of wash cycle to increase the persistent challenge of coating.
Water droplet absorbs test
Absorb (judging) required time fully and carry out water droplet and absorb test by applying the deionized water water droplet of 0.2mL and record water droplet to the surface of specimen according to range estimation from dropper.Unless otherwise mentioned, otherwise value is the mean value of three tests at diverse location place on the test article surface.If the water droplet soak time greater than 1 minute, stops test so and the record soak time is＞1 minute.
Case of comparative examples
Untreated samples (5cm * 5cm) carry out the water droplet absorption to test to Nomad 6000 ground cushions.The results are shown in the table 1.
Example 1(5nm surface modification Nano particles of silicon dioxide)
(Nalco 2326 by the dispersed with stirring liquid to the 5nm Nano particles of silicon dioxide, 33.3g, the 15wt% solid content) be incorporated in 2-hydroxyl-3-[3-(trihydroxy the is silica-based) propoxyl group in the 30g deionized water in] propane-1-sulfonic acid (36.7g, the 9.07wt% solid content) preparation surface modification Nano particles of silicon dioxide dispersion liquid, and obtain clear solution (pH=1.78 and silane coverage rate are 100%) after at room temperature 1 hour.(5cm * 5cm), then heated 1 hour down at 90 ℃ makes the ground cushion cooling that was coated with get back to environment temperature then be coated with Nomad 6000 ground cushion specimen on the padding mangles under 3kg pressure.Repeat to wash circulation back water droplet and absorb the results are shown in the table 1 of test.
Example 2(20nm surface modification Nano particles of silicon dioxide)
(Nalco 2327 by add the 20nm Nano particles of silicon dioxide in 40.6g water, 6.25g, the 40wt% solid content), under agitation add 2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group then] propane-1-sulfonic acid (3.13g), then 80 ℃ down heating 4 hours with obtain the pH value be about 2 and solid content be that the clear solution of 15wt% prepares surface modification Nano particles of silicon dioxide dispersion liquid.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 3(75nm surface modification Nano particles of silicon dioxide)
(Nalco 2329 by add the 75nm Nano particles of silicon dioxide in 42.9g water, 6.25g, the 40wt% solid content), under agitation add 2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group then] propane-1-sulfonic acid (0.81g), then 80 ℃ down heating 4 hours be that the clear solution of about 2 (15wt% solid contents) prepares surface modification Nano particles of silicon dioxide dispersion liquid to obtain the pH value.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 4(through organosilanol sulfonic acid and acrylate-silane-modified 20nm particle)
By to 15g 2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group] add 20nm Nano particles of silicon dioxide (Nalco 1034A in propane-1-sulfonic acid (5.7wt%), 29g, 34wt% solid content) and the 71g deionized water, then at room temperature stir 30 minutes, add 0.77g A174 and then stir 2 hours down to obtain translucent solution (10wt% solid content then at 50 ℃; Coverage rate: organosilanol sulfonic acid 50% and A17450%; PH=1.56) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 5(through the silane-modified 20nm particle of PEG-)
By in the 49g deionized water, add 20nm Nano particles of silicon dioxide (Nalco 2327,50g, 40wt% solid content), then add 6.2g SIM6492.7, then 90 ℃ down heating 2 hours to obtain clarifying coating solution (19wt% solid content; Coverage rate: 100%; PH=7.02) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Before the coating, use H
3PO
4Making solution be acidified to the pH value is 2.Described in example 1, dispersion liquid is coated on the specimen, and test result is showed in the table 1.
Example 6(through carboxyl-silane-modified 5nm particle)
By under agitation (Nalco 2326 to the dispersion liquid of 5nm Nano particles of silicon dioxide, 15.7g, the 15wt% solid content) in add the 4.35g deionized water, then add 0.94g SIC2263.0, at room temperature stirred 3 hours then and under 85 ℃, spend the night then to obtain clarifying coating solution (10wt% solid content; Coverage rate: 75%; PH=10.64) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Before the coating, use H
3PO
4Make solution be acidified to the pH value and be 2-3.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 7(through chlorosulfonyl phenyl-silane-modified 5nm particle)
By under agitation to the dispersion liquid of 5nm Nano particles of silicon dioxide (Nalco 2326, add in 66.7g) the 33.3g deionized water, then add 1g ethanol and 3.9g SIC 2417.0, at room temperature stirred 10 minutes and put into then 50 ℃ of baking ovens then and reach 1 hour to obtain clarifying coating solution (10wt% solid content; Coverage rate: 50%; PH=1.25) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 8(through chlorosulfonyl phenyl-silane-modified 20nm particle)
By under agitation (Nalco 2327 to the dispersion liquid of 20nm Nano particles of silicon dioxide, 25g, add in 40wt%) the 75g deionized water, then add 1g ethanol and 2.0g SIC 2417.0, at room temperature stirred 10 minutes and put into then 50 ℃ of baking ovens then and reach 1 hour to obtain clarifying coating solution (10wt% solid content; Coverage rate: 50%; PH=2.00) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 9(through organosilanol sulfonic acid and epoxy radicals-silane-modified 20nm particle)
By under agitation to dispersion liquid (the Nalco 1034A of 20nm Nano particles of silicon dioxide, 29g, 34wt% solid content) add 16.5g 2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group in] propane-1-sulfonic acid (solid content: 5.02wt%) and the solution of 35g deionized water, then add the solution of 1.46g KH560 in 36g water, at room temperature stir 24 hours to obtain semitransparent coating solution (8.07wt% solid content then; Coverage rate: organosilanol sulfonic acid 50% and KH560100%; PH=2.29) prepare surface modification Nano particles of silicon dioxide dispersion liquid.Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 10(adding the naked Nano particles of silicon dioxide of 5nm) through the 5nm of organosilanol sulfonic acid modified particle
To through 2-hydroxyl-3-[3-(trihydroxy is silica-based) propoxyl group] (Nalco 2326,16.9g, 5wt% solid content, coverage rate: 100% for the dispersion liquid of the Nano particles of silicon dioxide of propane-1-sulfonic acid surface modification; PH=1.94; About typical case preparation referring to example 1) in add the 16.9g acidifying the naked Nano particles of silicon dioxide of 5nm (Nalco 2326,16.9g, pH=1.81 uses H
3PO
4Regulate) and at room temperature stir the mixture 30 minutes to obtain clarification coating solution (5wt% solid content).Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Example 11(the unmodified Nano particles of silicon dioxide of 5nm)
By in the dispersed with stirring liquid (Nalco 2326,33.3g, 15wt% solid content) of 5nm Nano particles of silicon dioxide, adding the 67g deionized water, with nitric acid the pH value being adjusted to 2.39 then and preparing the Nano particles of silicon dioxide dispersion liquid.
Described in example 1 with this solution coat on specimen, and test result is showed in the table 1.
Table 1
Above-mentioned test and test result are only planned for illustrative but not predictability, but and the expected test program change and can produce Different Results.Above-detailed and example only provide for the clear purpose of understanding.It should be interpreted as unnecessary restriction.
Will be apparent concerning the those skilled in the art, in many examples, particular exemplary structure disclosed herein, feature, details, configuration etc. can be revised and/or make up.The present inventor expect all these variations and the combination all contain within the scope of the invention.Therefore, scope of the present invention should not be subjected to described certain illustrative structural limitations herein, and limited by the described structure of language of claims and the equivalent of these structures.Exist under the situation of contradiction or difference between the disclosure in this specification and any list of references of incorporating into way of reference herein, should be as the criterion with this specification.
Claims (20)
1. one kind for fibrous substrate provides the method for durable hydrophilic property coating, and described method comprises:
Thermoplastic fibre is contacted with coating composition, and described coating composition comprises:
Average grain diameter is the aqueous liquid dispersion of the following Nano particles of silicon dioxide of 100 nanometers or 100 nanometers, wherein
The pH value of the aqueous liquid dispersion of described Nano particles of silicon dioxide is less than about 3; With
It is dry so that the Nano particles of silicon dioxide coating to be provided on described thermoplastic fibre.
2. method according to claim 1, the concentration of Nano particles of silicon dioxide described in the wherein said coating composition are that 5wt% is to 20wt%.
3. method according to claim 1, wherein said thermoplastic fibre is hydrophobicity.
4. method according to claim 1, wherein said thermoplastic fibre comprise the thermoplastic resin that is selected from by polyamide, polyester, polypropylene, polyurethane, polyvinyl chloride, its blend and the group that forms.
5. method according to claim 1, the average grain diameter of wherein said Nano particles of silicon dioxide are about 20 nanometers or below 20 nanometers.
6. method according to claim 1, the average grain diameter of wherein said Nano particles of silicon dioxide are about 10 nanometers or below 10 nanometers.
7. method according to claim 1, the average grain diameter of wherein said Nano particles of silicon dioxide are about 5 nanometers or below 5 nanometers.
8. method according to claim 1, wherein said Nano particles of silicon dioxide comprises the surface modification Nano particles of silicon dioxide.
9. method according to claim 8, wherein said surface modification Nano particles of silicon dioxide comprises the surface modifier with following chemical formula:
[(Z)
c-R
3]
d-Si-(OR
4)
b(R
4)
4-(b+d)，
Wherein
Z is a hydrophilic radical;
R
3For covalent bond or randomly replaced by at least one oxygen atom and randomly by-divalence with about 1 to 20 carbon atom or trivalent hydrocarbon bridge linkage group that the OH base replaces; And
R
4Be hydrogen or alkyl, the aryl or aralkyl that randomly replace independently with 1 to 8 carbon atom through oxygen, nitrogen and/or sulphur atom;
C is 1 or 2, b be 1 to 3 and d be 1 or 2 and (b+d)≤4.
10. method according to claim 9, wherein Z is selected from the group that is made up of carboxylic acid group, sulfonic group, phosphonate group and its salt.
11. method according to claim 9, wherein Z is selected from the group that is made up of hydroxyalkyl and poly-hydroxyalkyl.
12. method according to claim 9, wherein Z is selected from the group that is made up of oxyalkylene group and polyoxyalkylenes.
13. method according to claim 9, wherein Z comprises quaternary ammonium group.
14. method according to claim 1, wherein said coating composition comprises
80wt% is to the water of 95wt%;
5wt% is 100nm or the Nano particles of silicon dioxide below the 100nm to the average grain diameter of 20wt%;
The pH value of wherein said coating composition is less than about 3.
15. according to the described method of arbitrary claim in the claim 1 to 14, wherein said pH value is less than about 2.
16. a hydrophily object, it is by method preparation according to claim 1.
17. hydrophily object according to claim 16, wherein measured as absorb test according to water droplet after at least 10 washing circulations carrying out according to the washing test, described object has less than about 10 seconds MAT.
18. hydrophily object according to claim 16, wherein measured as absorb test according to water droplet after at least 10 washing circulations carrying out according to the washing test, described object has less than about 5 seconds MAT.
19. hydrophily object according to claim 16, wherein measured as absorb test according to water droplet after at least 20 washing circulations carrying out according to the washing test, described object has less than about 5 seconds MAT.
20. according to the described hydrophily object of arbitrary claim in the claim 16 to 19, it is a ground cushion.
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|---|---|---|---|
| CN2009102029662A CN101892585A (en) | 2009-05-22 | 2009-05-22 | Method for manufacturing hydrophilic fiber article |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103660404A (en) * | 2012-09-24 | 2014-03-26 | 3M创新有限公司 | Hydrophilic film as well as preparation method and applications thereof |
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2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103660404A (en) * | 2012-09-24 | 2014-03-26 | 3M创新有限公司 | Hydrophilic film as well as preparation method and applications thereof |
| CN103660404B (en) * | 2012-09-24 | 2016-12-21 | 3M创新有限公司 | Hydrophilic film, its preparation method and application |
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