CN1260011A - Polyvinyl alcohol based nonwoven articles with vivid color and method of producing same - Google Patents

Abstract

Vividly colored absorbent articles useful as wiping articles and a method for their manufacture. A preferred article is characterized by (a) a nonwoven web comprised of organic fibers having a plurality of pendant hydroxyl groups; (b) a binder comprising a cross-linked polyvinyl alcohol and a hydrophobic polymer coated on at least a portion of the fibers, (c) pigment distributed within the binder.

Description

Brightly painted polyvinyl alcohol based nonwoven articles and manufacture method thereof

The present invention relates to durable painted suction nonwoven fabric wipe articles and the manufacture method thereof made with polyvinyl alcohol-based adhesives.

The background of invention

The height suction leather that is formed by the rawhides of the antelope of natural moccasin, similar goat or other animals and the wipe articles made are generally used for for example glazing or the drying after the car cleaning of some object.The absorbent properties that " synthetic moccasin " also can imitate natural moccasin, the goods of synthetic moccasin or wipe articles are for known to the public, and can buy.These synthetic products are for example to arrange net fiber non-woven bonding with adhesive and form.Fiber can comprise the PVA base fiber of for example using crosslinked polyvinyl alcohol (PVA) adhesive to be glued together.The PCT application WO94/28223 that announces has described the height suction wipe articles that comprises with the bonding non-woven fabric net of crosslinked PVA adhesive resin.Other known synthetic moccasins are non-woven fabrics fiber is glued together and makes with the acrylic emulsions adhesive.Suitable acrylic adhesives typically comprises gives adhesive and wipe articles finished product with the hydrophilic functional group.Though the manufacturing cost of these acrylic wipe articles is not high relatively, when being applied to many wipings, they usually stand do not wish to take place strong dilatory.

To add when synthesizing wipe articles with the adhesive that chemical crosslinking PVA makes, and can provide some tangible advantages.Wipe surfaces, excellent mechanical property and the desired absorbent properties of PVA adhesive by non-cotton wool is provided for example can improve and improve the performance of dry wipe product.In addition, the PVA adhesive can be cured in the presence of colouring agent, produces painted wipe articles.

In the manufacturing of synthetic moccasin or wipe articles, because attractive in appearance and practical or its function, it is painted requiring wipe articles usually.For example a certain color is being effective aspect the covering stain on the wipe articles surface.In addition, some countries comprise wipe articles for consumer's article, have developed the numbering system of color, wherein the colour code of article the use zone of being scheduled to, for example redness is used for the bathroom, green is used for kitchen etc.In these article painted, use pigment to be better than dyestuff usually, this is because in the presence of chemical cleaner, pigment can provide stronger fade resistance.

The common painted color of the basic wipe articles of the PVA that can buy is colour, by adding pigment or realizing as sour variable color result during making.Yet, use pigment so that painted more bright-coloured PVA base wipe articles to be provided, normally unsuccessful, this is because when wipe articles is exposed to water, especially have soap or washing agent to exist under the situation, these wipe articles can be taken off pigment constantly, are referred to as " loss of color ".The leakage of color owing to certain not by the adhesive resin stay fully admittedly and wipe articles in suds especially drenched or soak into during the loss of the pigment particles that discharges easily.From aesthetic, do not wish to take place the tangible pigment leakage on these article, the pigment that runs off on article can damage the surface that (promptly staiing) wants wiping.Though the color bleed problem can be avoided by the packing of wipe articles and the extensive washing before the use, the cost of manufacture height that this is additional, and can damage wipe articles.Therefore, and thereby prewashing goods before providing the method for staying pigment admittedly need not use in wipe articles are solved pigment losing issue in the PVA base wipe articles, there is a kind of demand.

Desiredly be: solution to the problems described above is provided, fills up this long-term demand blank by brightly painted PVA base wipe articles is provided.Desiredly be: adopt the technology of pigment coloring to provide such wipe articles, make when being exposed to water, when comprising the water that contains soap or washing agent, can not producing the obvious color loss in the goods.Also require to provide the method for making these wipe articles.

The general introduction of invention

The invention provides painted bright-coloured absorbing products that especially is used as wipe articles and preparation method thereof.These goods provide excellent wiping properties, but in use even when being exposed to suds etc., also do not produce significant color bleed.

In one aspect, the present invention is the absorbing products that comprises matrix, adhesive and pigment; Matrix contains the organic fiber that has many pendant hydroxyl groups; Adhesive is coated at least a portion fiber, and it contains the pure and mild hydrophobic polymer of crosslinked polyethylene; Pigment dispersing is in adhesive.Matrix optimization is the non-woven fabric net of organic fiber, and this fiber is selected from artificial fibre and polyvinyl alcohol.Polyvinyl alcohol (PVA) polymer can be formed by the homopolymers and the copolymer of the part or all of hydrolysis of vinyl acetate.The PVA polymer is preferably the PVA of silanol modification.Hydrophobic polymer is formed by the hydrophobic latex emulsion.Hydrophobic polymer is self-crosslinking polymer preferably.Pigment optimization is an organic pigment.

Just as used herein, " absorbability " speech refers to absorbed liquid (for example water) and retains liquid until the ability that is extruded; Very fast wetting ability when it refers to also that material is exposed to liquid." matrix " refers to woven, knitting or nonwoven cloth material." fiber " refers to the structure of wire (with reference to the fiber of the net that is used for making goods here, " line density " or " fineness " refers to the weight in grams number of filamentary specific length), " crosslinked " refers to monomer, prepolymer or the polymer chemical reaction of (being present in the precursor of adhesive for example), wherein is cross-linked to form between polymer chain." self-crosslinking " refers to by not adding crosslinking agent just can carry out reactant (for example monomer), prepolymer or the formed polymer of polymer of cross-linking reaction." pigment " refers to the insoluble material (being colouring agent) that is suspended in the medium.

On the other hand, the present invention is a method of making absorbing products, this method is by the matrix that contains the organic fiber that has many pendant hydroxyl groups being provided, providing absorbing products with pigment and adhesive precursor mixture coating at least a portion fiber and cure adhesive precursor, and adhesive precursor contains polyvinyl alcohol and hydrophobic latex emulsion.

On the other hand, the present invention is the absorbing products that comprises the matrix with first and second first type surfaces, matrix comprises the organic fiber that has many pendant hydroxyl groups, wherein at least one in first and second first type surfaces applies with the binder combination that contains the pure and mild hydrophobic polymer of crosslinked polyethylene, and pigment dispersing is in adhesive.

Brief description of drawings

When the details of explanation preferred implementation, with reference to various accompanying drawings, wherein:

Fig. 1 is the view of wipe articles constructed in accordance;

Fig. 2 is the cross sections of Fig. 1 goods along the 2-2 line; With

Fig. 3 is a block diagram of making the method for optimizing of goods of the present invention.

The detailed description of preferred embodiment

Goods of the present invention preferably are comprised of the matrix that contains organic fiber, and matrix contains the organic fiber with many pendant hydroxyl groups, and wherein at least part of fiber applies with the mixture of pigment and adhesive. The mixture of PVA and hydrophobic latex emulsion forms adhesive precursor, and this precursor cures is to form adhesive of the present invention. Since curing agent to exist PVA to carry out crosslinked. The hydrophobic latex emulsion is the emulsion of self-crosslinking preferably, and this do not need to refer to crosslinking agent. Be unexpectedly, the composition of crosslinked PVA and the hydrophobic polymer that formed by the hydrophobic latex emulsion has been made adhesive, and this adhesive can be retained pigment in the finished product of wipe articles, keep the color of finished commodities, prevents color bleed.

Matrix of the present invention can be fabric or nonwoven cloth material. Textile material comprises by the woven and knitting fabric of making. Nonwoven cloth material is thumb pad or net typically, by comprising that loop bonding, air lay, combing, technology spunbond, that melt and spray with wet-laying form.

Matrix of the present invention is non-woven fabric net preferably, and preferred non-woven fabric net has entangled fiber. Entangled fiber is tangled by for example water and the method for acupuncture bonding is made.

The typical thickness of matrix is about 0.25-2.54 millimeter (10-100 mil), preferred 0.76-1.78 millimeter (30-70 mil), more preferably 1.02-1.52 millimeter (40-60 mil). The weight per unit area of matrix preferably is about 50-250 gram/rice² Woven or knitted net can be made desired thickness and Unit Weight. Non-woven fabric net can be made by some technology with very thin, light layer. The preferred thickness of non-woven fabric net and Unit Weight can or by the operation of combing and cross lapping or by air lay, then realize by fibre matting (such as water entanglement, acupuncture bonding etc.). Combing is crossed and is intersected the net that spreads and also can tangle. Combing and the network optimization that spreads that intersects are selected in the goods of the present invention.

With reference to the accompanying drawings, Fig. 1 has shown absorbability wipe articles 10 of the present invention. Goods 10 comprise the non-woven fabric net of being made by many fibers 12, the mixture coating of at least part of fiber 12 usefulness pigment and adhesive, and the below can further specify. As shown in Figure 2, goods 10 (enlarging thickness shows) comprise respectively the first and second first type surfaces 14 and 16. Each of surface 14 and 16 contains the organic fiber of calendering and the coating of hot melt combination adhesive. More non-woven fabric net consists of the mid portion 18 of goods 10. The those of ordinary skill of the industry can be realized goods and can make like this: wherein only have a first type surface (for example surface 14) to use applying adhesive. Uncoated surface (i.e. surface 16) can be such as being laminated on another goods or matrix such as sponge, the polyurethane foam etc.

Non-woven fabric net can be made by any all hydrophilic fibres, can comprise part (for example being lower than about 50%) hydrophobic fiber.Hydrophobic fiber comprises polyamide fiber for example polyester, polypropylene and polyamide fiber.The suitable hydrophilic fibre that is used for here can be selected from following fiber type: the fiber of cellulose family, for example PVA (hydrolyzed copolymer that comprises the hydrolyzed copolymer of vinyl esters, especially vinyl acetate), cotton, viscose rayon, cuprammonium rayon etc.; Thermoplastic fibre, for example polyester, polypropylene, polyethylene, nylon etc.Preferred cellulosic fibre is artificial silk and polyvinyl alcohol (PVA), and can buy its staple fibre.Suitable rayon fiber be with 18552 and the T2222 title, available from the staple fibre viscose rayon of the Courtaulds Fibers Inc. of Alabama State, Axis.Other suitable rayon fibers are with " Lyocell " and " Tencel " trade mark, available from the fiber of Courtaulds Fibers Inc..Suitable PVA fiber comprises that those are with VPB152 and the VPB174 trade mark fiber available from Japanese Tokyo, Kuraray Co..

Within the scope of the invention, designed and contained 100%PVA fiber, 100% rayon fiber and PVA fiber and rayon fiber: 100-100: the non-woven fabric net that 1 ratio mixes with about 1, especially preferred in the present invention those PVA: the ratio of artificial silk is about 30: 70-70: 30 non-woven fabric net, this is because formed like this goods can show good hydrophily and intensity, and soft-touch.

Though also can use the higher fiber of dawn number, the line density that is commonly used to make the fiber of above-mentioned net is about 0.5-10 DENIER (about 0.06-11 dtex).(" dawn number " is the unit of line density or fineness, represent 9000 meters long stapled weight in grams numbers, and " dtex " is another unit of line density, the long stapled weight in grams number of expression ten thousand metres).Preferred fiber linear density is about the 0.5-3 dawn (0.06-3.33 dtex).The fiber that length can be about 0.5-10 centimetre is as the raw material of non-woven fabric net, and preferred fibre length is about 2-8 centimetre.

Be applicable to that the non-woven fabric net in the goods of the present invention can comprise air lay, combing, acupuncture bonding, wet-laying or melts and sprays and the spunbond technology manufacturing according to the method for very knowing.Preferred non-woven fabric net is the senior nonwoven cloth material of the air lay of the three-dimensional of opening wide, and people such as Hoover are in U.S. Patent No. 2,958, describes to some extent in 593, introduces here for your guidance.Air lay can the equipment that can buy for example " Rando Webber " machine (available from the Rando Machine Company in New York) go up or easily carry out by other conventional method.(seeing for example Turbak, " nonwoven fabric: senior guide " that A. published in the Tappi of the Atlanta of Georgia publishing house in 1989).

The major part of matrix fiber uses the adhesive that is solidified to form by adhesive precursor to be glued together.Solidify the cross-linking reaction that refers in the adhesive precursor, this is cross-linked to form insoluble adhesive.Be applicable to the hydrophobic polymer that the adhesive of the present invention in operating contains crosslinked PVA and formed by the hydrophobic latex emulsion.This hydrophobic polymer also can be crosslinked.The polymer that forms by the hydrophobic latex emulsion in the adhesive that solidifies preferably chemical bonding (for example by crosslinked) to PVA.Adhesive precursor preferably is made up of PVA, crosslinking agent and the hydrophobic latex emulsion of dissolving.

The PVA polymer can be partly or entirely formed by the homopolymers and the copolymer of the vinyl acetate of hydrolysis.The different PVA polymer of degree of hydrolysis, molecular weight and comonomer all is known, and can buy.For example: available from E.I.DuPont de Nemours Co., the trade mark " Elvanol " of Inc. (Wilmington, Delaware); Available from Air Products and Chemicals, the trade mark " Airvol " of Inc. (Allentown, Pennsylvania); Functional polymer available from the trade mark " KL-118, KL-318, KL-506, KM-118, C-118, C-506, C-318, HL-12E, HL-1203, HL-75, HL-1108, R-1130, R-2105 and R-2130 " of K, C, HL and the HL series of Kuraray Chemical KK (Japanese Tokyo).All these compositions that can buy all are applicable to the preparation adhesive precursor.

Preferred PVA is the homopolymers of part or all of hydrolysis or the copolymer that is formed by first and second monomer copolymerizations.First monomer can be selected from: the monomer of general formula (I):

Wherein X is Si (OR ⁴OR ⁵OR ⁶);

Second monomer is selected from the monomer of general formula (II):

Wherein Y is O (CO) R ⁷, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷Be independently selected from hydrogen and the organic group that has 1-10 carbon atom.

The PVA of preferred silane alcohol modification especially in adhesive of the present invention.The PVA of suitable silanol modification can form with unsaturated ethylene linkage monomer copolymerization alkoxy silane-replacement by any in many unsaturated ethylene linkages that have a hydrolyzable groups.The non-limitative example that has the unsaturated ethylene linkage monomer of hydrolyzable groups is vinyl acetate, acrylic acid acetoxyl group ethyl ester, methacrylic acid acetoxyl group ethyl ester and various propyl acrylate and methacrylates.The unsaturated ethylene linkage monomer of alkoxy silane-replacement comprises vinyl trialkyl oxysilane for example vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl three butoxy silanes etc.The preferred vinyl trimethoxy silane.

A kind of PVA of particularly preferred silanol modification can be by the copolymerization of vinyl acetate and vinyltrimethoxy silane, then copolymer direct hydrolysis (face explanation as follows) in alkaline solution is formed.The known brands of the suitable silanol modified PVA that can buy is " R1130 " (Kuraray Chemical KK, Japan), think that it contains the silicyl as the vinyl silanes unit of the 0.5-1.0% that has an appointment (mole), its degree of polymerization is about 1700, and the degree of hydrolysis of vinyl acetate unit is about 99% or higher.

In adhesive precursor, PVA mixes with suitable and compatible with PVA crosslinking agent.Suitable crosslinking agent comprises any various known crosslinking agent, for example comprises: aldehyde, vulcabond, polyacrylic acid and various metal complex be the chelate of aluminium, titanium, silicon, zirconium etc. for example.For example described various PVA crosslinking agents in 272-277 and the 282-285 page or leaf in the John Wiley andSons publishing house in New York in 1992 " development of polyvinyl alcohol " book that publish, that C.A.Finch edits, here introduced for your guidance.The selection of suitable crosslinking agents is the operating technology in field of the present invention normally.Yet, when selecting to be used for the suitable crosslinking agents of goods of the present invention, should consider the final color of desired goods.Requiring under the chromatic colour situation, do not needing the crosslinking agent of requirement strongly acidic catalyst usually.Therefore, formaldehyde and other single and two-aldehyde are not preferred cross-linking agents usually, especially under low PH condition.

Preferred PVA adopts the organic titanium of chelating to produce crosslinked as crosslinking agent by the secondary hydroxyl that is positioned on the PVA main chain.In theory, the adhesive of formation can be further when hot setting with fiber on hydroxyl reaction.Especially preferred is " two-fold " crosslinked PVA polymer, and wherein amorphous metal oxide is also as crosslinking agent, with when above-mentioned titanium and the secondary hydroxyl coordination, carries out coordination with the silanol on the PVA main chain.Useful especially amorphous metal oxide is the trade mark that can buy is less than about 30 dusts for the particle mean size of " Nalco 8676 " (Nalco Chemical, Naperville, Illinois) an amorphous state alumina sol.

Particularly preferred PVA polymer is those polymer that use the organic titanium cross-linking agent of above-mentioned amorphous metal oxide and chelating, this crosslinking agent or contain two (amine lactic acid) titaniums of dihydroxy (available from the E.I.DuPont de Nemours Co. of Delaware, Wilmington, Inc. the trade mark " Tyzor LA "), the ortho esters (available from E.I.DuPont de Nemours Co., the trade mark of Inc. " Tyzor 131 ") that perhaps contains titanium.

Can be positioned at the scope of about 1-40% (mole) for the theoretical crosslink density of suitable PVA polymer, be benchmark with the molal quantity of unsaturated ethylene linkage monomer.

As mentioned above, adhesive contains by the formed polymer of the emulsion in the adhesive precursor.When finished product for example is exposed to suds then, be contained in emulsion in the adhesive precursor at the solid pigment that is in the finished product retained to avoid having shown important effect aspect the color bleed.Unexpectedly, use the polymer that forms by the hydrophobic latex emulsion admittedly stay the interior pigment of adhesive to invariably accompany, and need not sacrifice desired finished product absorbent properties.

Be not subjected to the constraint of any particular theory, think that color bleed mainly can result from the loss of smallest particles pigment (being usually less than about 0.1 micron).In the manufacture process of the goods that contain the PVA adhesive, use the adhesive precursor of solids content low (for example in water, being lower than 15%) usually.In adhesive precursor, granule pigment is considered to lose the surface-activity of their association, causes the cohesion of particle.The granule that forms is excessive, can not reside in the adhesive of curing.The result works as the finished product goods and disperses just to have produced the loss of color in the entry with suds cleaning, pigment granule again.The operation of known hybrid pigment is being invalid aspect the reduction color bleed phenomenon.The existence that has been found that self-crosslinking hydrophobic latex emulsion can promote the combination of pigment particles in the emulsion.Successively, pigment particles just easily in conjunction with entering in the adhesive of finished product, reduces color bleed widely.In addition, this pigment runs off reduce greatly and use less hydrophobic polymer is to take place together.

Preferred hydrophobic latex emulsion is the emulsion that polymer is provided when solidified, and this polymer combines with PVA and/or matrix fiber by this way: (for example be exposed to suds) under humidity or the wet condition and can stop migration in case be exposed to.Preferred emulsions is can be crosslinked, forms water-fast crosslinked polymer, and this polymer can stop efficiently and washed away from finished product.Preferred emulsion is a self-crosslinking, and most preferred emulsion is a self-crosslinking, again can with PVA with covalent bonds.If emulsion is a hydrophobic, for the purpose of firm, emulsion be coated to surperficial going up form film, then dry and curing.The wetting tension on surface is relevant with the hydrophobicity on surface.This can adopt the surface tension of water or more specifically by measuring a water and surperficial formed contact angle is measured.For the purposes of the present invention, if to be considered on the cured film of emulsion be hydrophobic to emulsion, the advancing contact angle of water is approximately greater than 45 ° so.

The content of emulsion in adhesive precursor is about 0.05-20% (weight) (is benchmark with the drying solid).The concentration of emulsion is higher than about 20% (weight) in the adhesive precursor, is considered to harmful to the absorbability of finished product.Concentration is lower than about 0.05% (weight), is not enough to stay admittedly the pigment in the adhesive.The preferred content of emulsion is about 1-15% (weight) (is benchmark with the drying solid) in the adhesive precursor.The preferred content of emulsion is about 3-10% (weight) (is benchmark with the drying solid).Hydrophobic polymer just can not move away on flexible finished product like this, and especially when moistening, the glass transition temperature of hydrophobic polymer (Tg) should be lower than about 5 ℃, preferably is lower than about 0 ℃, more preferably less than-15 ℃ approximately.

The suitable example that is used for hydrophobic latex emulsion of the present invention includes but is not limited to: acrylate-based emulsion, for example copolymer of butyl acrylate, ethyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, styrene, N hydroxymethyl acrylamide etc.; Polyurethane, polyester and polyamide.The emulsion of the present invention that is used for that can buy comprises that the trade mark is " Rohamere 132 ", " Rohamere 1878 ", " Rohamere 1900-D ", " Rohamere 1970-D ", " Rohamere 3045 ", " Rohamere31-130 ", " Rohamere 4096D ", " Rohamere 587 ", " Rohamere 84116 ", " Rohamere8437 ", " Rohamere 8464 ", " Rohamere 8478 ", the acrylic acid ester emulsion of " Rohamere 8662 " and " Rohamere87219 ", all these is available from Rohm Tech Inc. (Malden of Massachusetts).For operation of the present invention, the acrylic emulsions that many kinds have a suitable physical is the trade mark " Rhoplex " available from the Rohm and Haas Co. of Pennsylvania, Philadelphia.Vinyl acetate/vac emulsion with suitable physical can buy with the trade mark of " Airflex ", the polyvinyl acetate ester homopolymer can buy with " Vinac " trade mark, the both is available from the AirProducts and Chemicals of Pennsylvania, Allentown, Inc..Preferred hydrophobic latex emulsion comprises with the B.F.Goodrich Co. styrene-propene acid butyl ester of the trade mark " Hycar T-278 " available from Ohio, Akron, with the trade mark " RhoplexE-2744 " and " Rhoplex NW-1845 " acrylic emulsion available from Rohm and Haas Co..The suitable hydrophobic latex emulsion that will recognize that other also can be used for preparing adhesive precursor.

Adhesive precursor contain the PVA of dissolving solution, be preferably the aqueous solution, crosslinking agent and hydrophobic latex emulsion.Adhesive precursor can be the solid that content is about 1-60% (weight), preferably is about 2-20% (weight).Adhesive precursor is preparation so typically: at first dissolving PVA in the water, add crosslinking agent, then stir and add the hydrophobic latex emulsion.

Before condition of cure (being high temperature) occurs, should avoid the crosslinked of PVA and emulsion.When using the titanate esters crosslinking agent, can add for example citric acid of organic acid to adhesive precursor, to help the titanate esters (for example two (ammonium lactic acid) titaniums of dihydroxy) in the stable composition aqueous solution, be exposed to crosslinked and condition of cure until adhesive precursor.If make the crosslinking agent (for example aldehyde, amino resin) of acid activation, then can require in adhesive precursor, to add for example Diammonium phosphate (DAP) of potential acid.

Pigment mixes with adhesive precursor.Being used for pigment of the present invention comprises inorganic and organic pigment.Inorganic pigment is often referred to superfine metal oxide or sulfide.Inorganic pigment is not a solubility.They can be highly colored with as colouring agent, for example white, as opacifier.Organic pigment typically refers to the highly colored material into carbon back rather than Metal Substrate.For the purposes of the present invention, when organic compound was given the desired color of goods, it was a pigment, and when making or using goods of the present invention, it is insoluble to employed solvent.

Preferably the aqueous dispersion system of pigment as superfine particle added in the adhesive precursor.Typical particle size is changed to about 10 microns from sub-micron.Dispersion system promotes the dispersion of pigment in adhesive.The suitable aqueous dispersion of organic pigment is to buy.They comprise weaving and picture art pigment type, available from comprising Sun Chemical Co. (Fort Lee, the New Jersey), Heucotech Ltd. (Fairless Hills, the Pennsylvania), Catawba Char-Lab (Charlotte, the North Carolina), Organic DyestuffsCo. (Charlotte, the North Carolina), Penn Color (Doylestown, Pennsylvania) and BASFCorp. (Wyandotte, Michigan).Also can prepare pigment according to the known method of the industry.

Suitable pigment comprises and is not limited to: organic pigment, AZO pigments for example, as solvable or insoluble AZO pigments or concentrated AZO pigments, phthalocyanine color, quinoline a word used for translation ketone pigment, dihydroindolone pigment, perylene-perynone? pigment, dioxazines pigment, reduction stain pigment and basic dyeing pigment, and inorganic pigment, for example carbon black, titanium oxide, chrome yellow, cadmium yellow, cadmium red, red iron oxide, iron oxide black, zinc flower?, Prussian blue and ultramarine.Usually, preferred organic pigment, this is because they do not contain heavy metal, for example chromium, lead, tin and/or barium.

Except above-mentioned composition, also need in adhesive precursor, to add optional ingredients.Such optional member comprises softener (for example ether and alcohol), spices, filler (for example silica, aluminium oxide and TiO 2 particles) and bactericide (for example quaternary amine).These compositions in the adhesive precursor and their relative ratios will become with chemical characteristic and its predetermined effect of composition, and those of ordinary skill in the art will be easy to realize this point.

In the method for the invention, provide matrix with institute's required thickness and weight per unit area.Apply to the mixture of small part matrix with adhesive precursor and pigment, the dry and adhesive precursor that is heating and curing is forming adhesive and pigment to small part matrix.

See Fig. 3 now, illustrate the method (as illustrated in fig. 1 and 2) of making preferred matrix, non-woven fabric net.In the process of preparation non-woven fabric net, staple fibre is fed combing website 22 by charging aperture 20 (or additive method).Mobile conveyer is delivered to the cross lapping machine (not shown) usually with the net 26 self grooming websites 22 of combing, forms layered web, on it fiber with respect to the machine direction of carded web 26 with various angular orientation.Then, carded web 26 makes fibre matting through acupuncture bonding website 28, thereby strengthens and consolidate net, and forms acupuncture adhesive net 30.The entanglement of net also can by the method beyond the acupuncture bonding for example water tangle and realize.

Acupuncture adhesive net 30 can randomly be passed through calender website 32, obtains desired thickness, and press polish net 34 is provided, and the preferred thickness of this net 34 is no more than about 1.52 millimeters (60 mils).Then, press polish net 34 applies the mixture of pigment and adhesive precursor herein through dipping bath 36.Below the net 34 process rollers 38, the net 40 for applying when occurring.Can also can comprise roller coating, spraying, intaglio printing coating, shift coating etc. by immersing coating method by other known coating methods of the industry with adhesive precursor coating net.During coating, apply the part fiber at least, preferably apply the one side at least of first and second first type surfaces of net with pigment and adhesive precursor mixture.Preparation as the process of hand with wipe articles etc. in, two first type surfaces of coating net typically.The poly-percentage that is reported as the weight of Wiping articles finished product of coating amount (weight) (being the coating amount of dry adhesives).Coating amount is about 1-95%, preferably is about 10-60%, is more preferably 20-40%.

The net 40 that applied forms dry net 44 through super-dry website 42.When dry website 42, net typically and preferably is exposed under the high temperature, removes the water in the adhesive precursor, and forms dry net 44.Drying can use hot-rolling (i.e. " heat jar "), forced ventilation baking oven, radiant panel or other known methods to implement.Preferably evenly dry on the whole thickness of net.According to the type of the crosslinking agent of adhesive precursor composition, use, moisture etc., net 44 does not need further curing just to be suitable for using.

Typically and preferably require at first to carry out drying, follow the cure adhesive precursor.By as mentioned above at first dry net implement this two step process.The then dry net of crossing 44 is through last curing website 42.Solidifying website, be exposed to high temperature and come cure adhesive, form net 48 dry and that solidify.The drying of adhesive precursor and curing can realize that mode is for example dry and curing schedule to be implemented by dry net 44 is exposed to plural different temperatures in the baking oven with two above heating tapes.In addition, when dry and cure adhesive precursor, two first type surfaces of uncured net preferably are exposed to thermal source simultaneously.Although be less preferred, first and second first type surfaces of coating net also can be exposed to thermal source in order.

Then net 48 can be through another to felt wrapped roll 50, and it can be used for extruding pattern, the surface of fusion goods.The thickness of net 52 is no more than 1.52 millimeters (60 mils) usually, and weight is about 50-250 gram/rice ²Adhesive coating net carries out press polish under about 5-40 ℃ the temperature that is lower than the fiber fusing point, can reduce the probability that burlap is attached to product surface, and can provide smooth surface usually.The fabric weave pattern that is depressed on the Wiping articles can be carried out with press polish or carry out in subsequent step simultaneously.

In order to decorate or other purpose, then can carry out punching to net with net 52 through the second optional acupuncture website 54.Then, net is broken away, and is wound up on the take up roll 56.

Net 52 also can be bathed (not shown) through superheated water (promptly about 60-80 ℃) before being broken away and being wound up on the take up roll 56, and as mentioned above by press polish of hot-rolling type and drying, made soft " hand " sense or sensation.The another kind of mode that obtains soft feel and help to process on final packing articles is just before packing, and applies the solution of a spot of water and fungicide immediately to goods.If necessary, cured article can laminate or differently be attached to another matrix for example sponge, polyurethane foam backing etc.In using, can require to use and have only the cured article that has adhesive on the first type surface, can be applied adhesives etc. so undressed first type surface (surface that does not promptly have cure adhesive) is provided.

Goods of the present invention are because its absorbability and durability especially are suitable for work " synthetic antelope ".These synthetic Wiping articles are of great use to cleaning various surfaces.The existence of pigment in the goods, make that goods become that the consumer uses attractive in appearance, joyful and have the wipe articles of absorbent function.The goods preferred heights is painted, can be made into the articles colored of the easy identification that is used for cleaning a certain zone (for example green is used for the kitchen).Goods manufactured according to the present invention in use show the leachability on the minimum color own product.

Embodiment has illustrated the preparation that is suitable for the net that is used as absorbing products with adhesive and pigment coating.

The explanation of material

In an embodiment, use some material according to following abbreviation and trade mark sign.

Preparation section

Following preparation section is used for preparing the goods that are identified in embodiment.

Operation A (preparation of matrix)

By 50% artificial fibre (3.0 dawn * 6.3 centimetre, T2222, Courtaulds Fibers Inc. (Alabama, and 50% vinal (1.7 dawn * 5.3 centimetre Axis)), VPB174, Kuraray Co.KK (Japan, Tokyo)) prepares non-woven fabric net.Non-woven fabric net is sprawled preparation by combing and intersection, and to provide Unit Weight through acupuncture be 162.9 gram/rice ²(4.8 oz/yd ²), thickness is the net of 1.45 millimeters (57 mils).For following embodiment, net is to be of a size of the sheet coating of 38.1 centimetres of 30.5 cm x (12 inches * 15 inches).Therefore in the preparation of non-woven fabric net, the orientation of fiber depends on it and how to be made into, and referring to forming the direction of " machine " or the downward net of contrast with " net laterally " direction, net horizontal direction and machine direction are orthogonal thereto.

Process B (PVA solution)

Coating solution prepares like this: heat the extremely boiling of 9.3 parts of polyvinyl alcohol (available from " R1130 " of Kuraray Co.KK) in 90.7 parts of deionized waters, make the PVA dissolving.Add (0.44 part of amorphous alumina sol to PVA solution, " Nalco 8676 " available from Nalco Chemical Co.), (" Tyzor131 " is available from the E.I.DuPont de Nemours Co. of Delaware, Wilmington, Inc.) then to add 4.4 parts of titanate esters.Cool off formed solution, then be diluted to that solids content is 3.6% (weight) when 121 ℃ (250 °F) are dry with deionized water.

Operation C (adhesive precursor and wipe articles)

Emulsion and pigment are added in the PVA solution with the ratio described in the embodiment, as described in embodiment, add deionized water simultaneously.PVA solution and emulsion form adhesive precursor.The mixture of pigment and adhesive precursor to matrix, is uniformly dispersed by hand, makes the matrix of coating.Then, the matrix of coating is carried out air drying under 65.6 ℃ (150 °F), until drying, and is heating and curing 10 minutes under 149 ℃ (300 °F).The drying on the matrix and the amount of cured polymer (being adhesive) are about 18% (weight).

Method of testing

Method of testing is estimated the wipe articles of embodiment below using.

Color bleed

Color bleed is measured like this: at first take off the material sample that will estimate, put into 2 premium on currency, it was soaked 60 seconds.Then sample is twisted out, and in washbasin, contain rinse water with hand.For the every kind of material sample that will test, all repeat to soak and twist out step 20 time.Afterwards, observe and write down the color color and the dense shallow degree on cleaning fluid and basin surface, with the sample cell of 10 centimetres of optical lengths on ultraviolet-visible spectrophotometer, the visible absorption spectrum of measurement and record rinse water.

Then cleaning solution is poured out in basin, put into 2 liters of clear water again.Fully sample is twisted out, on sample, put 2 gram washing agent (available from the Alconox in New York, New York, " Liquinox " trade mark of Inc.), on the most surfaces of sample, gently rub.The sample of handling is like this put into clear water.Then twist out and have washing agent/aqueous mixtures and return sample in the basin again with hand.Sample soaks once more and twists out for the second time, as mentioned above, with the sample cell of 10 centimetres of optical lengths, measures the visible absorption spectrum of rinse water.

TENSILE STRENGTH

The preparation sample soaks in water and twists out with machinery that machine is disposable to twist out, and tests.Sample is die-cut into 2.54 * 15.24 centimetres (1 * 6 inches).

Use strength tester (available from the Instron model " TM " of the Instron Corp. of Massachusetts, Canton), adopt the improvement program of the described method of testing of ASTM D 5035-95 " fracture strength of textile fabric and the standard method of test of elongation " (band method) to measure TENSILE STRENGTH.Also write down sample thickness.Stretch with constant rate of speed, clamping element is the clamp class.The speed that clamp separates is 25.4 cm per minute (10 inch per minute clocks).Sample is put into clamp, fix, begin circulation and measure with the spacing of 2.5 centimetres (1 inches).TENSILE STRENGTH (load) when measuring fracture and elongation.TENSILE STRENGTH is represented the rigidity of sample.Extension at break is the tolerance that increases until the load of sample breakage that applied and continuous.Test in sample upper edge machine direction and net horizontal direction, this is because mechanical property can become with the direction of orientation.

Bleach stability

The wipe articles immersion is contained the 286 gram mixtures of 5.25% (weight) chlorine bleach (family expenses concentration chlorine bleach is available from " Clorox " trade mark of the Clorox Co. that adds livre Buddhist nun Asia, Oakland) in the solution of 14 liters of running water.When sample took out in liquid lime chloride, eyesight was estimated fading of its color.

Ai Er gateway husband formula is torn test

The preparation sample soaked 5 minutes in low-grade fever water, and machinery twists out then, the test tear resistance.

It is to adopt available from Thwing-Albert Co. that Ai Er gateway husband formula is torn test, model be the Ai Er gateway husband formula tearability tester of 60-32, use 6.4 kilogram pendulum, on the sample of jagged (20 millimeters) of 6.35 * 27.94 centimetres that punch out (2.5 * 11 inches), carry out.Program is the improvement program of the described method of testing of ASTM D 1424-96 " by the standard method of whereabouts pendulum class (Ai Er gateway husband formula) instrument test fabric tearing strength ".Write down the mean value of four tests.Along machine direction and horizontal both direction specimen.Tearing strength is represented the durability of absorbing products of the present invention.

Absorbability

Absorbability test is in the low-grade fever water that at first sample is immersed in basin or other containers 15 minutes, and then sample twists out through machinery and removes most of water.When still moist, cut out the rectangle material of 20.3 centimetres of 15.2 cm x (6 inches * 8 inches).The material that is cut into is put into the water of basin low-grade fever once more, its was soaked 15 minutes.Filter screen is placed on the below of the sample that is cut in the basin.After 30 seconds, in basin, mention filter screen and the sample that is cut into, sample is taken off on filter screen, be put on the weighing pan immediately with the action of quick and stable with pincette.This operation requires the analyst that certain technology is arranged, and should carry out this operation always, until obtain rule ± reappearance of 1 gram.The reading of recording balance (gram), it is total water absorption/nothing drip (A).Other samples that cut out are repeated this program.

The sample of handling like this that is cut into is immersed in the basin of low-grade fever water 5 minutes.Afterwards, sample is taken out in water, then use the spring clip that is attached to ring-shaped support to hang one jiao with pincette.After 60 seconds, each sample all is transferred to weighing pan with the action of quick and stable.The reading of recording balance (gram), it is total water absorption W/ drip (B).Other samples that cut out are repeated this program.

The sample that cuts out is put into once more the basin 5 minutes of low-grade fever water.Afterwards, each sample is taken out in water, twist out machine through machinery with single thickness.Action with quick and stable is transferred to weighing pan with sample.The reading of recording balance (gram), it is weight in wet base (C).Other samples that cut out are repeated this program.

Then the sample that cuts out is put into the baking oven at least 12 hours that force ventilated, temperature remains in 49 ℃ (120).Once the sample that will reach 6 takes out in baking oven, and weigh immediately (gram), and be recorded as dry weight (D).Repeat this program for other samples that cut out.

Then calculate percentage, absorbability and effective absorbability of dehydration according to following formula:

Dehydration percentage=100 * (A-B)/B;

Absorbability (the gram number/dry weight of water)=(A-D)/D;

Effective absorbability (gram number/rice of the water of absorption ²)=32.292 * (A-C).

Wearability test

To be present in the dry and curing of hydrophobic latex emulsion in the adhesive precursor, form the polymer of common ABRASION RESISTANCE expection than independent PVA polymer difference.For the influence to ABRASION RESISTANCE of emulsion that adding is described, adopting H22 Calibrade wheel, model that 500 grammes per square metres are housed is that 503 Taber Abraser instrument is tested ABRASION RESISTANCE.The preparation sample is soaked in them in the low-grade fever water, and machinery strand sample 4 times, to remove whole excessive moistures.When visible hole (0.3 centimetre of (1/8 inch) diameter) occurring on the sample, the record destructiveness.

Embodiment

The characteristic of goods of the present invention and advantage will further be illustrated in the following non-limiting Examples.

Comparative Examples A

Matrix prepares red wipe articles described in the use operation A.It applies with 139 gram PVA solution (preparing as mode as described in the process B) and the organic red of 0.6 gram (available from " Orcobrite Red BRYN 6002 " trade mark of the Organic Dyestuffs of North Carolina, Charlotte) and 61 mixtures that restrain deionized waters.Dry and the curing sample application in the described mode of operation C.

Comparative example B

Matrix prepares blue wipe articles described in the use operation A.It applies with organic blue pigment of 0.5 gram (buy the trade mark and be " Orcobrite Blue 3GN 2010 ") and 61 mixtures that restrain deionized waters with 139 gram PVA solution (preparing as mode as described in the process B).Dry and the curing sample application in the described mode of operation C.

Comparative example C

Matrix prepares green wipe articles described in the use operation A.It applies with organic green pigment of 0.3 gram (buy the trade mark and be " Orcobrite Green YN9 ") and 61 mixtures that restrain deionized waters with 139 gram PVA solution (preparing as mode as described in the process B).Dry and the curing sample application in the described mode of operation C.

Embodiment 1

This embodiment illustrates the preparation of red wipe articles.Fiber web prepares sample described in the use operation A.It uses the adhesive precursor mixtures that prepared by 132 gram PVA solution (preparing as mode as described in the process B), 0.45 gram emulsion (" Hycar T-278 "), the organic red of 0.6 gram (trade mark is " Orcobrite Red BRYN 6002 ") and 67 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The wipe articles that forms contain 5% (is benchmark with dried solid) by the formed polymer of emulsion in the adhesive (" Hycar T-278 ").

Embodiment 2

This embodiment illustrates the preparation of red wipe articles.Fiber web prepares sample described in the use operation A.It uses the adhesive precursor mixtures that prepared by 125 gram PVA solution (preparing as mode as described in the process B), 0.91 gram emulsion (" Hycar T-278 "), the organic red of 0.6 gram (trade mark is " Orcobrite Red BRYN 6002 ") and 74 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The wipe articles that forms contain 10% (is benchmark with dried solid) by the formed polymer of emulsion in the adhesive (" Hycar T-278 ").

Embodiment 3

This embodiment illustrates the preparation of red wipe articles.Fiber web prepares sample described in the use operation A.It uses the adhesive precursor mixtures that prepared by 118 gram PVA solution (preparing as mode as described in the process B), 1.36 gram emulsions (" Hycar T-278 "), the organic red of 0.6 gram (trade mark is " Orcobrite Red BRYN 6002 ") and 80 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The wipe articles that forms contain 15% (is benchmark with dried solid) by the formed polymer of emulsion in the adhesive (" Hycar T-278 ").

Embodiment 4

This embodiment illustrates the preparation of blue wipe articles.Fiber web prepares sample described in the use operation A.It uses the adhesive precursor mixtures that prepared by 125 gram PVA solution (preparing as mode as described in the process B), 0.91 gram emulsion (" Hycar T-278 "), the organic blue pigment of 0.5 gram (trade mark is " Orcobrite Blue 3GN 2010 ") and 74 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The wipe articles that forms contain 10% (is benchmark with dried solid) by the formed polymer of emulsion in the adhesive (" Hycar T-278 ").

Embodiment 5

This embodiment illustrates the preparation of green wipe articles.Fiber web prepares sample described in the use operation A.It uses the adhesive precursor mixtures that prepared by 125 gram PVA solution (preparing as mode as described in the process B), 0.91 gram emulsion (" Hycar T-278 "), the organic green pigment of 0.3 gram (trade mark is " Orcobrite Green YN9 ") and 74 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The wipe articles that forms contain 10% (is benchmark with dried solid) by the formed polymer of emulsion in the adhesive (" Hycar T-278 ").

Below table 1 provided the detailed results of analytical test gained changes of properties.

Comparative Examples A-C and embodiment 1-5

The extension test result:

As method test tensile strength as described in the method for testing of above-mentioned TENSILE STRENGTH.Intensity and elongation are tested along horizontal (direction 2) of the net of machine direction (direction 1) and sample during fracture.Do not observe the obvious deterioration of tensile property, show that adding hydrophobic latex emulsion (" Hycar T-278 ") only causes small infringement.

Table 1

Extension test

Embodiment	Orientation	The peak-peak (pound/inch) of load	Standard deviation	The elongation % at peak-peak place	Standard deviation
						Comparative Examples A	Direction 1	????29.8	????1.9	????60	????2
The same	Direction	2	????38.1	????2.5	????75							????3
						????1	Direction 1	????35.5	????0.7	????68	????4
The same	Direction	2	????38.4	????1.2	????76							????3
						????2	Direction 1	????30.6	????1.4	????70	????4
The same	Direction	2	????37.3	????1.8	????75							????3
						????3	Direction 1	????32.9	????1.2	????63	????8
The same	Direction	2	????41.2	????2.5	????78							????4

Bleach stability

According to the wipe articles that Comparative Examples A and embodiment 2 make, test according to above-mentioned bleach stability method of testing.When sample took out in bleaching liquid, the immersion sample of Comparative Examples A was compared with the color rank of its non-immersion wipe articles, existing fading; And the immersion sample of embodiment 2 keeps bright-coloured redness, and fading of appearance is less.Do not observe and use of the negative effect of emulsion additive bleach stability.

Before being exposed to bleaching liquid and afterwards, these samples are carried out extension test twice.Test data is as shown in table 2.

Table 2

Extension test

(bleaching sample)

Embodiment	Orientation	The peak-peak (pound/inch) of load	Standard deviation	The loss % of tensile load
					Before the bleaching
Comparative Examples A	Direction 1	????29.8	????1.9
						Direction 2	????38.1	????2.5
????2	Direction 1	????30.6	????1.4
						Direction 2	????37.3	????1.8
In 2% bleaching liquid 8 hours
					Comparative Examples A	Direction 1	????13.1	????1.0	????56
	Direction 2	????15.2	????1.0	????61
					????2	Direction 1	????17.3	????0.9	????43
	Direction 2	????21.4	????2.3	????43

Tear test result:

To the goods of Comparative Examples A and embodiment 1-3, test described method according to above-mentioned Ai Er gateway husband formula tearability and tear test.Test data is as shown in table 3.Data show by the existence of the formed polymer of hydrophobic latex emulsion does not have detrimental effect to the ABRASION RESISTANCE of sample.

Table 3

Embodiment	Orientation	On average	Standard deviation
				Comparative Examples A	Direction 1	????68	????15
	Direction 2	????89	????7
				Comparative Examples A	Direction 1	????76	????15
	Direction 2	????80	????11
				????1	Direction 1	????76	????11
	Direction 2	????73	????14
				????2	Direction 1	????69	????10
	Direction 2	????67	????11
				????2	Direction 1	????74	????18
	Direction 2	????76	????16
				????3	Direction 1	????74	????14
	Direction 2	????88	????8

The absorbent properties test

Absorbability according to above-mentioned absorbability method of testing test shows: by the formed polymer of hydrophobic latex emulsion absorbability is not significantly influenced.Test data is as shown in table 4.

Table 4

Absorbent properties

Embodiment	Percentage of water loss %	Absorbability (the gram number of the gram number/dry-eye disease of water)	Effective absorbability (gram number/the foot of the water of absorption 2)
				Comparative Examples A	????16.54	????6.42	????90.57
Comparative Examples A	????16.16	????5.79	????84.00
				Embodiment 1	????14.34	????6.23	????90.90
Embodiment 2	????17.42	????6.39	????97.95
				Embodiment 2	????14.57	????6.14	????87.69
Embodiment 3	????17.60	????6.41	????87.96

Wearability test

The destruction of record sample when visible hole (0.32 centimetre of (1/8 inch) diameter) occurring according to abrasion resistance test method.Test data is as shown in table 5.Data show that the polymer that formed by the hydrophobic latex emulsion does not have detrimental effect to the ABRASION RESISTANCE of sample.

Table 5

Wearability test

Embodiment	To the period of destroying
		Comparative Examples A	????1228
????1	????1126
		????2	????1419
????2	????1677
		????3	????1668

Color bleed

As described below, wipe articles carries out the color bleed test.Under red, the blue and green wipe articles situation of Comparative Examples A, B and C, after twisting out, in water, observe very heavy color bleed, when having washing agent and twisting out, observe serious color bleed.On the contrary, contain at wipe articles under the situation of 10% or more emulsion of adding, the sample that has washing agent in most cases, can detect faint color after twisting out.The result who adds 5% " Hycar T-278 " emulsion occupies between the result who adds 0-10%.

Each sample is as shown in table 6 in the data at the denseest absorbing wavelength place of color.

Table 6

Color bleed

Embodiment	Wavelength (nanometer)	Absorption after water cleans	Absorption after soap cleans	The reduction rate of color bleed
					Comparative Examples A	????525	????0.4062	????1.0285	????NA
????1	????525	????0.0377	????0.1759	????91
					????2	????525	????0.0149	????0.0875	????83
????3	????525	????0.0093	????0.1008	????90
					Comparative example B	????625	????0.5034	????0.8764	????NA
????4	????625	????0.0110	????0.0374	????96
					Comparative example C	????650	????0.2986	????1.0900	????NA
????5	????650	????0.0318	????0.0932	????91

Comparative example D

Matrix prepares red wipe articles described in the use operation A.It applies with organic red of 0.3 gram (buy the trade mark and be " Orcobrite Red BRYN 6002 ") and 61 mixtures that restrain deionized waters as the PVA solution that mode as described in the process B prepares with 152 grams.Dry and the curing sample application in the described mode of operation C.The curing wipe articles inner binder content that forms is 14% (is benchmark with dried solid).

Embodiment 6

Fiber web prepares red wipe articles described in the use operation A.It uses the adhesive precursor mixtures that prepared by 137 gram PVA solution (preparing as mode as described in the process B), 1.2 gram emulsions (" Rhoplex NW-1845 ", non-crosslinked emulsion), 0.63 gram organic red (" Orcobrite Red BRYN 6002 ") and 61 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The curing wipe articles inner binder content that forms is 15%.

Embodiment 7

Fiber web prepares red wipe articles described in the use operation A.It uses the adhesive precursor mixtures that prepared by 137 gram PVA solution (preparing as mode as described in the process B), 1.2 gram emulsions (" Rhoplex ST-954 ", acrylic acid self-crosslinking latices emulsion), 0.63 gram organic red (" Orcobrite Red BRYN 6002 ") and 61 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The curing wipe articles inner binder content that forms is 15%.

Embodiment 8

Fiber web prepares red wipe articles described in the use operation A.It uses the adhesive precursor mixtures that prepared by 137 gram PVA solution (preparing as mode as described in the process B), 1.2 gram styrene-butadiene self-crosslinking latices emulsions (" Unocal 4170 "), 0.64 gram organic red (" Orcobrite Red BRYN 6002 ") and 61 gram deionized waters to apply.Dry and the curing sample application in the described mode of operation C.The curing wipe articles inner binder content that forms is 15%.

Comparative example D and embodiment 6-8

According to above-mentioned color bleed method of testing, estimated the color bleed of embodiment 6,7,8 and comparative example D goods.Observed embodiment 6,7 and 8 color bleed significantly are lower than comparative example D.

Though discuss and describe in detail better embodiment of the present invention, do not breaking away under the connotation scope of the present invention that claims set forth, the those of ordinary skill of the industry will be realized and can carry out changes and improvements to described embodiment.

Claims (43)

1. absorbing products, it contains:

(a) contain the matrix of the organic fiber that has many pendant hydroxyl groups;

(b) be coated on adhesive at least a portion fiber, this adhesive contains crosslinked polyvinyl alcohol and hydrophobic polymer;

(c) be scattered in the interior pigment of adhesive.

2. absorbing products as claimed in claim 1, wherein said matrix contains non-woven fabric net.

3. absorbing products as claimed in claim 2, the weight of the unit are of wherein said non-woven fabric net is about 50-250 gram/rice ²

4. absorbing products as claimed in claim 1, wherein said organic fiber contains the material that is selected from polyvinyl alcohol and artificial fibre.

5. absorbing products as claimed in claim 4, the ratio of wherein said vinal and artificial fibre are 30: 70-70: 30.

6. absorbing products as claimed in claim 1, wherein said polyvinyl alcohol are silanol modified polyethylene alcohol.

7. absorbing products as claimed in claim 6, wherein said silanol modified polyethylene alcohol is crosslinked with the metal complex of chelate that is selected from aluminium, titanium, silicon and zirconium and composition thereof.

8. absorbing products as claimed in claim 1, wherein said hydrophobic polymer is formed by the self-crosslinking latices emulsion.

9. absorbing products as claimed in claim 1, wherein said hydrophobic polymer is formed by the hydrophobic latex emulsion that with the material that is selected from acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N hydroxymethyl acrylamide, polyurethane, polyester and polyamide is base.

10. absorbing products as claimed in claim 9, wherein said acrylate is selected from butyl acrylate, ethyl acrylate and methyl methacrylate.

11. absorbing products as claimed in claim 1, the glass transition temperature of wherein said hydrophobic polymer are lower than 0 ℃.

12. absorbing products as claimed in claim 1, the glass transition temperature of wherein said hydrophobic polymer are lower than-15 ℃.

13. absorbing products as claimed in claim 1, the content of wherein said hydrophobic polymer are the 1-15% (weight) of adhesive.

14. absorbing products as claimed in claim 1, wherein said pigment is organic pigment.

15. absorbing products as claimed in claim 1, wherein said polyvinyl alcohol are the cross-linked copolymers of a kind of cross-linked homopolymer of hydrolysis or the hydrolysis that formed by first and second monomer copolymerizations, first monomer is the monomer of general formula (I): Wherein X is Si (OR ⁴OR ⁵OR ⁶);

Second monomer is the monomer of general formula (II):

Wherein Y is O (CO) R ⁷, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷Be independently selected from hydrogen and organic group with about 1-10 carbon atom.

16. absorbing products as claimed in claim 15, wherein said polyvinyl alcohol carries out crosslinked with the crosslinking agent that is selected from aldehyde, vulcabond, polyacrylic acid, metal complex and composition thereof.

17. absorbing products as claimed in claim 16, wherein said metal complex are selected from the chelate and the composition thereof of aluminium, titanium, silicon and zirconium.

18. absorbing products as claimed in claim 15, wherein said polyvinyl alcohol adopts organic titanate as crosslinking agent, undertaken crosslinkedly by the secondary hydroxyl on the main polymer chain, silanol on the main polymer chain adopts metal oxide to carry out crosslinked as another crosslinking agent.

19. make the method for absorbing products, this method comprises:

(a) provide the matrix that comprises the organic fiber that has many pendant hydroxyl groups;

(b) with pigment and adhesive precursor mixture coating at least a portion fiber, described adhesive precursor contains polyvinyl alcohol and hydrophobic latex emulsion;

(c) solidify described adhesive precursor, so that absorbing products to be provided.

20. method as claimed in claim 19, wherein said step (a) comprise further that also it is that combing is crossed and intersected the matrix of the non-woven fabric net sprawled that form is provided.

21. method as claimed in claim 19, wherein said step (a) comprise further that also it is the matrix of non-woven fabric net that form is provided, this non-woven fabric net has first and second first type surfaces, and by the acupuncture bonding organic fiber in the non-woven fabric net is tangled.

22. method as claimed in claim 21, the weight of the unit are of wherein said non-woven fabric net is about 50-250 gram/rice ²

23. comprising with adhesive precursor, method as claimed in claim 19, wherein said applying step (b) apply in first and second first type surfaces of described non-woven fabric net at least one.

24. method as claimed in claim 19, wherein said organic fiber comprises the material that is selected from polyvinyl alcohol and artificial fibre.

25. method as claimed in claim 24, the ratio of wherein said polyvinyl alcohol and artificial fibre are 30: 70-70: 30.

26. method as claimed in claim 19, wherein said hydrophobic latex emulsion contains self-crosslinking polymer.

27. method as claimed in claim 19, wherein said hydrophobic latex emulsion is based on the material that is selected from acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N hydroxymethyl acrylamide, polyurethane, polyester and polyamide.

28. method as claimed in claim 27, wherein said acrylate is selected from butyl acrylate, ethyl acrylate and methyl methacrylate.

29. method as claimed in claim 19, the content of wherein said hydrophobic latex emulsion are the 1-15% (weight) of adhesive.

30. method as claimed in claim 19, wherein said pigment is organic pigment.

31. method as claimed in claim 19, the polyvinyl alcohol in the wherein said adhesive precursor are a kind of homopolymers or the copolymer that formed by the copolymerization of first and second monomers, first monomer is the monomer of general formula (I):

Wherein X is Si (OR ⁴OR ⁵OR ⁶);

Second monomer is the monomer of general formula (II): Wherein Y is O (CO) R ⁷, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷Be independently selected from hydrogen and organic group with about 1-10 carbon atom.

32. method as claimed in claim 31, wherein said adhesive precursor also further comprise the crosslinking agent compatible with polyvinyl alcohol, described crosslinking agent is selected from aldehyde, vulcabond, polyacrylic acid, metal complex and composition thereof.

33. method as claimed in claim 32, wherein said metal complex are selected from the chelate and the composition thereof of aluminium, titanium, silicon and zirconium.

34. method as claimed in claim 31, wherein said curing schedule (c) comprises cross-linking reaction, wherein said polyvinyl alcohol adopts organic titanate as crosslinking agent, undertaken crosslinkedly by the secondary hydroxyl on the main polymer chain, silanol on the main polymer chain adopts metal oxide to carry out crosslinked as another crosslinking agent.

35. comprise the absorbing products of the matrix with first and second first type surfaces, described matrix contains the organic fiber that has many pendant hydroxyl groups, wherein at least one in first and second first type surfaces is with containing following mixture of ingredients coating:

(a) contain the crosslinked polyvinyl alcohol and the adhesive of hydrophobic polymer;

(b) be scattered in the interior pigment of adhesive.

36. absorbing products as claimed in claim 35, wherein said matrix comprises non-woven fabric net.

37. absorbing products as claimed in claim 36, the weight of the unit are of wherein said non-woven fabric net is about 50-250 gram/rice ²

38. absorbing products as claimed in claim 36, wherein said organic fiber comprises the material that is selected from polyvinyl alcohol and artificial fibre.

39. absorbing products as claimed in claim 36, wherein said polyvinyl alcohol are silanol modified polyethylene alcohol.

40. absorbing products as claimed in claim 39, wherein said silanol modified polyethylene alcohol usefulness is selected from the chelate of aluminium, titanium, silicon and zirconium and the metal complex of composition carries out crosslinked.

41. absorbing products as claimed in claim 36, wherein said hydrophobic polymer is formed by the hydrophobic latex emulsion that with the material that is selected from acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N hydroxymethyl acrylamide, polyurethane, polyester and polyamide is base.

42. absorbing products as claimed in claim 36, the content of wherein said hydrophobic polymer are the 1-15% (weight) of adhesive.

43. absorbing products as claimed in claim 36, wherein said pigment is organic pigment.

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