CN101184812A - Nanoparticle containing, pigmented inks - Google Patents

Nanoparticle containing, pigmented inks Download PDF

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Publication number
CN101184812A
CN101184812A CNA2005800499381A CN200580049938A CN101184812A CN 101184812 A CN101184812 A CN 101184812A CN A2005800499381 A CNA2005800499381 A CN A2005800499381A CN 200580049938 A CN200580049938 A CN 200580049938A CN 101184812 A CN101184812 A CN 101184812A
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CN
China
Prior art keywords
fabric
composition
coupling agent
coating
silane
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Pending
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CNA2005800499381A
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Chinese (zh)
Inventor
K·森伍
文秀珍
赵贞菊
李妵娙
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Kimberly Clark Worldwide Inc
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Kimberly Clark Worldwide Inc
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Publication of CN101184812A publication Critical patent/CN101184812A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/3081Treatment with organo-silicon compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673Inorganic compounds
    • D06P1/67383Inorganic compounds containing silicon
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22Effecting variation of dye affinity on textile material by chemical means that react with the fibre
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30Ink jet printing
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/06Ethers; Acetals; Ketals; Ortho-esters

Abstract

Provided is a new composition, printed fabrics and method for improving color strength and crock fastness on printed or coated polymeric, silk and cotton fabrics. The novel printing composition is an aqueous mixture having silica nanoparticles and silane coupling agents in addition to pigments and a relatively small amount of binder. The nanoparticles and coupling agent are preferably in a ratio of from about 1:3 to 3:1. The binder may be present in an amount between about 0.1 and 10 weight percent. A number of other optional ingredients like humectants, dispersants, biocides and the like may be present. Also provided is a method of making the printed fabric including the steps of mixing nanoparticles and coupling agent, adding water, pigment and binder and milling the mixture to a particle size between about 150 and 200 nm, applying the composition and drying the printed fabric.

Description

The pigment inks that comprises nano particle
Background technology
Tinctorial strength and the fastness of pigment inks on textiles normally controlled by the amount that joins the polymer bonding agent in this China ink mixture.But, realize that by the adding that increases caking agent pigment inks good fastness on fabric printing or coating does not have " feel " of this fabric or the unfavorable variation of flexibility is very difficult.When the amount of polymer bonding agent is high enough to show favorable durability (or fastness), the feel hardening of fabric or coarse.Keep the feel of fabric constant if reduce the amount of caking agent, then can not realize good fastness, especially crocking fastness.
Textiles (weaving or adhesive-bonded) is used for the wide variety of applications from clothes, handkerchief and urine fabric to the automobile cover.These application requiring have the material of different performance and quality.But some application requiring fabrics are height moisture absorptions; for example diaper and feminine hygiene articles liner; with require as fabric such as the clothes soft; perhaps have as the absorptivity as diaper and the towel; and other application requiring intensity; for example textile protection such as car and ship cover, and other application requiring repellency and barrier property such as the directed fabric of medical science as, for example sterilization overcoat and surgical operation robe.
Although it is uncorrelated and different that all application of fabric seem, a kind of common feature is to wish they are printed in some mode.This printing may be in order to make advertisement, identification of product, decoration, covering stain or the like purpose.Unfortunately, because the environment for use of many fabrics is not developed complete successful print system, most of concrete print system at room temperature moves.
Therefore a target of the present invention provides a kind of use, solidified printing (China ink) composition of at room temperature being easy to, and when said composition is exposed to most of common cleaning chemical and is in most of working conditions following time, it will be retained on the fabric, that is, it has high tinctorial strength and friction resistant decolouring fastness.A kind of textiles that the printing composition that provided prints and method that the described composition printing textile of a kind of usefulness is provided used is provided another one target of the present invention.
The invention summary
The present invention relates generally to a kind of new composition and be used to improve tinctorial strength on polymkeric substance, silk fabric and cotton fabric printing or coating and the method for crocking fastness.
This novel printing composition is to have except the caking agent of pigment and relatively small amount, also has the aqueous mixture of nano SiO 2 particle and silane coupling agent.The preferred ratio of this nano particle and coupling agent is about 1: 3-3: 1.This caking agent can exist with the amount in about 0.1-10 weight percentage ranges.Many other optional members such as wetting agent, dispersion agent, biocide etc. also can exist.
Said composition can be administered on the fabric and drying by many technology.Fabric can be compound fabric, nonwoven fabric, melt blown fabric, textile fabric and the laminating material spunbond and the melt blown fabric of water acupuncture manipulation slurry (hydroentangled pulp) and spun-bonded fibre.This textile fabric can be cotton, silk, polyester or nylon.
The present invention further comprises the printed fabric of the dried residue that has the composition that water-based uses thereon, and composition described here has nano particle, silane coupling agent, caking agent and China ink.
A kind of method of making this printed fabric also is provided, comprise step: nano particle and coupling agent are mixed, add entry, pigment and caking agent, and this mixture is ground to particle size is about 150-200nm, uses said composition and dry described printed fabric.
Invention specifically describes
The inventor has been found that by using a spot of polymer bonding agent and nano SiO 2 particle and silane coupling agent can realize black good color fastness and strong tinctorial strength.The inventor has been found that the silane coupling agent of the nano SiO 2 particle of about 0.1-10 weight percent and 0.5-20 weight percent can improve the crocking fastness and the tinctorial strength of the pigment inks system with vinylformic acid or polyether polyols with reduced unsaturation caking agent.
Composition of the present invention can be by many modes well known in the art such as screen printing, digital printed, dip-coating, spin coating or spray application to hydrophobic and hydrophilic fabric for example polyester, polyolefine, cotton, nylon, silk or the like, and this fabric can be textile fabric or nonwoven fabric.
Here without limits to the basic weight of the black employed fabric of described novelty or composition.Therefore, operable textile fabric and nonwoven fabric, the fabric that comprises bonded carded fabric, nonwoven fabric or melt blown fabric and comprise slurry is as being described in the United States Patent (USP) 5284703 those, and the one embodiment is the material of the commercial Hydroknit_ of being called.This kind fabric can be the specific embodiments of individual layer or be the composition of layer laminates that this layer laminates can comprise use tackiness agent, needle punching, heat viscosity method, form by air any other method bonding and well known in the art by many different laminations.
Do not wish to be confined to any specific theory, the inventor believes that silane coupling agent can carry out crosslinked and this coupling agent between organic polymer and inorganic silicon dioxide nano particle interpolation can improve the weather resistance of the fabric that is coated with and the tinctorial strength of Geng Gao.For example vinylformic acid and polyurethane adhesive improve fastness ability to traditional ink formulations by adding the polymer bonding agent.But, significantly do not concern between the amount of the caking agent that inventor's discovery is added and the crocking fastness raising amount.The same discovery of the inventor does not only improve crocking fastness significantly with the polymer bonding agent that nano SiO 2 particle uses together.But silica dioxide granule and silane coupling agent can improve the adhesive effect of polymer bonding agent vinylformic acid for example as follows and polyurethane adhesive.The inventor believes that nano SiO 2 particle and silane coupling agent can be by in crosslinked the bonding of polymer bonding agent of improving between polymkeric substance and the polymkeric substance or between polymkeric substance and the pigment or between polymkeric substance and the fabric face.
Crocking fastness is according to AATCC testing method 8-1996, (127mm * 178mm) material piece of test is measured in CM-5 type rub resistance look firm tester by placing one 5 inches * 7 inches, CM-5 type rub resistance look firm tester can be from Atlas Electric Device Company (4114Ravenswood Ave., Chicago IL60613) obtains.This rub resistance look firm tester is comforted the described sample surfaces predetermined times of wiping away or rub with fixed strength back and forth with cotton.To compare from color and the target that this sample is transferred on the cotton then, wherein 5 be illustrated on this cotton and do not have color, 1 is illustrated in and has a large amount of colors on this cotton.The non-fading relatively more sample of high more numeral.It is described that relatively target can be from American Association of Textile Chemists and Colorists (AATCC), PO Box12215, and Research Triangle Park, NC27709 obtains.
Tinctorial strength (K/S) uses Hunterlab Miniscan XE-Plus spectrophotometer to measure, and it can be from Reston, the Hunter Associates Laboratory of VA, and Inc. (hunterlab.com) obtains.If they have the Δ E greater than 3 *Value, the difference between the then similar color can quantize comparison.About this point, L *a *b *The measurement of colour and Δ E *Calculating (CIE 1976 Commission Internationale deI ' Eclairage) can use Hunterlab Miniscan XE-Plus spectrophotometer, carry out according to operational manual.Average optical adopts the average sum of using each spectral filter to measure for three times usually.Δ E *Calculate according to following equation:
Δ E *=SQRT[(L *Standard-L *Sample) 2+ (a *Standard-a *Sample) 2+ (b *Standard-b *Sample) 2]
Δ E *High more, the variation of colour intensity is big more.Test can be carried out according to ASTM DM 224-93 and ASTME308-90.Here for the ground of matte finish, Δ E *Value is generally acknowledged that such colour-change/difference can not observe with the naked eye usually less than 3.0.The detailed description of photodensitometer test can be published at AATCC (American Association of Textile Chemists and Colorists) in 1997 Color Technology in the Textile IndustryObtain in the second edition.
Nano particle used herein is a nano SiO 2 particle, and it carries out modification to give the user specified property of expectation by adding metallic molecule such as aluminium, silver, copper, nickel and gold.These performances comprise that water-repellancy, antimicrobial acivity and surface tension change.
Metal-modified nano SiO 2 particle is by with nano particle with comprise metal ion solution and mix and to prepare.Such solution is normally by being dissolved into metallic compound in the solvent, forms the free metal ion and make in this solution.Because potential difference, described metal ion is sucked out and is adsorbed onto on this nano particle.The further discussion of modified by nano particles can be found in the U.S. Patent application of submitting on April 30th, 2,002 10/137052, and it is hereby incorporated by.
Can utilize many technology between this transition metal and silica dioxide granule, to form stronger chemical bond.For example, it has been generally acknowledged that silicon sol at pH greater than about 7, be stable when particularly pH is for 9-10.When water-soluble, the salt of transition metal is tart (for example cupric chloride has about 4.8 pH).Therefore, when so acid transition metal salt mixed mutually with alkaline silica sol, pH was lowered, and metal salt precipitate is to the surface of silica dioxide granule.This injures the stability of this silica dioxide granule.In addition, under lower pH value, the reduced number of the silanol that on this silica particles, exists.Therefore because transition metal is attached on these silanol, this particle has been lowered in conjunction with the ability of transition metal under lower pH value.Also metal and silica dioxide granule bonding may be formed " coordination " and/or " covalent linkage ", this can have multiple benefit, as has reduced that any metal will keep the free possibility as described in use (for example after cleaning).
Because the pH that the adding of acid transition metal salt (for example cupric chloride) causes reduces the influence of effect, what can expect is in order to improve, with transition metal mixing process in, to the selective control of carrying out of silica dioxide granule pH.Selective control to pH can be by using any finishing in the multiple known buffer system known in the art.
Many suitable metal-modified nano SiO 2 particles are commercial obtainable.These comprise from Tokyo Nissan Chemical Industries, Ltd., SNOWTEX_-C, the SNOWTEX_-AK of Inorganic Material Division and SNOWTEX_-OXS nano particle.
Generally speaking, described silane coupling agent can be covalently attached on the silica dioxide granule by the silanol (Si-OH) that is present on the silica particles.Particularly, the Siliciumatom of this silane coupling agent can form covalent linkage with the oxygen of silanol.In case this silane coupling agent is covalently bound to silica dioxide granule, this organo-functional group just can form coordinate bond with transition metal.For example, copper can form coordinate bond with the different amino group that exists in the aminopropyl triethoxysilane coupling agent.Silane is well known in the art differing materials to be bonded to useful coupling agent on glass.For example, silane coupling agent is used in for a long time in the glass industry to add between the resin that wherein plays enhancement on the glass surface with glass and is formed chemical bond.In this bonding, generally believe between the Siliciumatom of the Siliciumatom of silane coupling agent and glass to form chemical bond or sucking action, and form chemical bond or sucking action between the hydrocarbon of this silane coupling agent part and this hydrocarbon resin.This covalent bonding theory is further shown at Edwin P.Pluedemann Silane Coupling Agents,Plenum Press, NY, NY, 1991 second editions make further research in the 18-22 page or leaf.Therefore, some surprisingly silane coupling agent will improve or improve the China ink color fastness.
Useful in the present invention silane is to comprise those of hydrocarbon part, i.e. organosilane comprises those of organoalkoxysilane and following formula:
R 1
|
Z-Si-R 2
|
R 3
Wherein Z represents vinyl, allyl group or other two key groups that can react, R under the radical polymerization condition 1, R 2And R 3Be reactive for example methoxyl group, oxyethyl group and other alkoxy bases, amino, epoxy group(ing), urea groups and vinyl groups, Cl or Br halogen, ester class for example the acetoxyl group or-O-Si or inertia group for example alkyl or aromatic hydrocarbon group.Three R groups can be all identical or different, but at least one R group must be reactive, and purpose is as the hydrolysis reaction agent.
Some examples of suitable operable organofunctional silane coupling agent comprise, but be not limited to vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl dimethyl dichlorosilane (DMCS), the vinyl methyl dimethoxysilane, the vinyl methyldiethoxysilane, 5-hexenyl Trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-(methyl) acryloxy propyl group methyldiethoxysilane, 4-ethenylphenyl Trimethoxy silane, 3-(4-ethenylphenyl) propyl trimethoxy silicane, 4-ethenylphenyl methyltrimethoxy silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-(2-amino-ethyl) TSL 8330,3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl group methyldiethoxysilane, and partial hydrolysate.
These silane have many suppliers, comprise HuIs America Inc., Chisso Corp., OSISpecialties Inc. and Dow Corning Corporation.Exemplary silane used herein comprises the 3-glycidoxypropyltrime,hoxysilane (GPTS) (CAS 2602-34-8) that obtains with trade name SILO-ACE S-510_ from Japanese Chisso Corporation; With from W1, (3-aminopropyl) triethoxyl silane (APTES) (CAS 919-30-2) that Milwaukee Sigma-Aldrich Chemical obtains.
Used in the present invention silane should be with the amount of the 0.01-10 weight percent of it being sneaked into thermoplastic polymer wherein and is existed.The amount that more specifically, it has been found about 0.1-2.5 weight percent is gratifying, and the amount of about more in particular 1 weight percent still.
Though silane can also be the solid of powder or particle form, useful in the present invention silane is liquid usually under room temperature and pressure, therefore makes mixing process simple relatively.
Be applicable to that caking agent herein comprises vinylformic acid, urethane and polyester adhesive,, can use the known any suitable caking agent of preparation printing ink those skilled in the art although more generally.Exemplary caking agent comprises Soluryl R40 and Snowtex series caking agent (seeing table 2).This caking agent can be with the 0.1-10 weight percent of millbase, more particularly the about amount of 4-7 weight percent and existing.
Pigment refers to the component with particulate colouring agent, but not as the liquid in the dyestuff.Can be used in pigment in the invention process comprise any can be found with described prescription in the pigment of used nano particle, coupling agent and caking agent active responding.The non-exclusive example of such pigment comprises that carbon black, enacol indigo plant, emacol fuchsin, irgaphore pigment, carbojet Huang and printofix are red.
The preparation method of new ink composition of the present invention can be begun by the surperficial addition of coupling agent to nano SiO 2 particle.This is by being that 6-8 is more particularly at about 7 o'clock in room temperature and pH, and with 3: 1 to 1: 3, more especially 2: 1 to 1: 2, the most about 1: 1 ratio was sneaked into silane coupling agent and finished with nano particle.The mixing of this nano particle and coupling agent produces thermopositive reaction, depends on the amount of existing reactant, and this reaction will be carried out a few hours under 60-70 ℃ temperature, get back to room temperature at last.
Prepare the pigment grind base-material by mixing the coupling agent modified nano particle prepare above and pigment, dispersion agent (if desired), caking agent and water and any desired optional member then.With grinding bead, often be 0.3 or the Zr pearl of 0.4mm diameter, joining in this pigment grind base-material and grinding this mixture is about 150-200mm up to particle size.The ultimate density of this mixture is the about 15-20 weight percent that accounts for China ink.
Then if desired, this millbase is mixed with more water, wetting agent, biocide, corrosion inhibitor and the capillary tensio-active agent of adjusting usually.Wetting agent comprises polyoxyethylene glycol (PEG) 200,400,600, glycerol, glycol ether (DEG) and 2-Pyrrolidone (2-pyrolididone).After this step, this China ink has the concentration of about 3-5 weight percent.
This China ink can be applied on textiles or the fabric and at about 110-120 ℃ and carries out drying then.Although because after thoroughly dewatering, can obtain the thermal-setting of better fabric, therefore recommend to carry out independent drying step, solidify processing and also can carry out and the drying-free step.
There are many methods that China ink is administered to fabric can be used in the practice of the present invention.Can use any other suitable method that well known to a person skilled in the art.Exemplary non-exclusive method comprises the preceding measuring system and the back measuring system of following concise and to the point description:
Preceding measuring system (China ink of initial use is inexcessive):
Slit mouth mould: this method is used the pressure head that wherein has slit.The coating material metering is passed through this slit directly to ground.
Directly intaglio printing: coating is in the loculus in the intaglio printing roller.Ground directly contact with this intaglio printing roller and with the pigment transfer in the loculus to ground.
Have the offset printing intaglio printing that contrary roller shifts: similar with direct intaglio printing, except the intaglio printing roller arrives the another one roller with pigment transfer.This second roller contacts with ground then.
Curtain coating: this is a kind of dispense tip that wherein has a plurality of slits.The different coating materials meterings of forming are by these slits and with before ground contacts, the given distance of dripping.
Slide (stepwise) be coated with: this method is similar to curtain coating, except multi-layer coated material from the dispense tip ground that comes out directly to contact.Between dispense tip and ground, there is not open gap.
Front and back roller coat (being also referred to as the transfer roller coating): this is made up of a pile roller, and its purpose for metering is transferred to next roller with coating material from a roller.Last roller contacts with ground.It is the sense of rotation that roller coat cloth or reverse roll coating forward will be depended on the travel direction and the last roller of ground.
Extrusion coated: this technology type is similar to slit mouth mould, except coating material at room temperature is solid-state.Material is heated to melt temperature and passes through slit directly to ground as liquid meter in dispense tip.By cooling, this material becomes solid again.
Roto-sifter: coating material is pumped in the roller with sieve surface.Scraper plate in this roller extrudes coating material through this sieve, then it is transferred to ground.
Nozzle is used: the coating material pressurized directly is sprayed onto on the ground by nozzle.Can apply the coating (preceding metering method) of desired amount.Perhaps ground can ooze by nozzle is full, then any unnecessary material is extruded (back metering method) by mip rolls.
Flexographic typography: the raised design surface of coating material being transferred to roller.This then pattern roll is transferred to coating material on the ground.
The printing of digital textile product: coating or printing ink are in the ink-jet tube.The fabric ground is delivered under this printing ink gun, China ink is sprayed onto on this ground makes printed images.
Back metering when initial (use excessive China ink, remove subsequently):
Rod is coated with machine: coating material is administered to substrate surface and uses rod that unnecessary material is removed.The Mayer rod is to be mainly used to measure the method for removing these unnecessary coating.
Air knife blade coating: coating material is administered to substrate surface and removes unnecessary coating material by using high-pressure air that it is purged.
Blade coating: coating material is administered to substrate surface and excess stock is removed by cutter structure head.
Scraper coating: coating material is administered to substrate surface and excess stock is removed by flat scraper structure head.
Dip-coating (infiltration) is followed by extrusion roll: ground is immersed in the used material.Then saturated ground traction is squeezed out unnecessary material by two rollers.
Spin coating: make applied ground high speed rotating.To also unnecessary material be thrown away the edge on the ground of this rotation of coating material paint.
The damping coating: coating material is by on the quilt damping head paint ground of filling with.Unnecessary material is removed by scraper.
Brush: coating material is by on the brush paint ground.Unnecessary material is controlled along moving of substrate surface by this brush.
In order to improve the crocking fastness of China ink, printed fabric then must be by " curing ".Curing is the process that this fabric is exposed to the environment of enough humidities under the temperature and time that is enough to make crocking fastness to increase.The type and thickness and the environmental factors that depend on the textiles ground are solidificated in about 150-200 ℃ and carry out the sufficiently long time.For example cotton is in 3 minutes set time of 180 ℃ of needs.Nylon is 150 ℃ of needs 3 minutes, and PET is in 3 minutes set time of 180 ℃ of needs.(should be noted that this time is proximate)
The embodiment of pigment grind base-material: China ink, caking agent, nano particle do not contain coupling agent
Make pigment grind base-material (table 1) and be used for the fastness of comparison after adding 5 kinds of different caking agents.In these examples, do not add coupling agent in the mixture.These adhesive polymers are listed in the table below in 2.
Table 1
The pigment grind base-material The gram number that adds Weight percent
Carbojet Yellow 270Y (10.1 weight percent) 30.15 18.6
Snowtex_-AK (nano SiO 2 particle) 30.24 18.6
Solsperse 44000 (dispersion agent) is from Lubrizol Inc. 2.01 1.2
Water 100.03 61.6
Summation 162.43 100
Table 2
Caking agent (all from INI DaeYoung Chemical Co.) Effect
Snotex PUW The water dispersible polyurethane emulsion
Snotex UW250 The water dispersible polyurethane emulsion that is used for cotton, regenerated fiber and blend fiber thereof
Snotex CPU2001 The crocking fastness improving agent that is used for Blue Jean pigment dyeing, urethane
Snotex NPU 1077N The water dispersible polyurethane emulsion
Snotex 890L The water-dispersion acrylate copolymer caking agent that is used for pigment
Every kind in 5 kinds of different polymkeric substance in the table 2 are joined in the pigment grind base-material (going up table 1) with 1 weight percent, and estimate tinctorial strength (K/S) and crocking fastness.A kind of do not have the reference examples of adhesive polymer to test yet.Described polymkeric substance joined in the pigment grind base-material (pigment+Solsperse as shown in table 1 (dispersion agent)+Snowtex AK) and Polyester Twill fabric is immersed in the described pigment grind base-material that has/do not have a polymer bonding agent, each carries out drying and solidified 3 minutes at 180 ℃ at 120 ℃.
After the curing, this fabric is cleaned the loose pigment on the surface of removing this polyester textile in tap water.Come evaluate color friction resistant fastness and tinctorial strength (K/S) by the polyester textile that uses this cleaning.
Result in the table 3 shows with the pigment grind base-material that does not contain caking agent and compares that crocking fastness and tinctorial strength all do not have significantly to improve.
Table 3
Additive Particle Drying at room temperature After 180 ℃ of curing
Snotex- Size (nm) K/S Crocking fastness K/S Crocking fastness
1 890L 462.90 13.34 1.5 22.54 1.0
2 CPU2001 398.00 7.09 2.5 24.56 1.5
3 NPU1077 402.90 7.63 2.5 10.54 1.5
4 UW250 320.70 8.10 2.5 20.79 2.0
5 PUW 511.60 9.84 2.5 13.06 1.5
6 Do not have 24.80 9.48 2.5 20.78 2.0
The other example that polymkeric substance is added in the pigment to improve crocking fastness is shown in the following table 4.The Emacol Blue pigment of solution from Japanese Sanyocolor Inc., Snowtex_-AK nano SiO 2 particle (in certain embodiments) and from the Soluryl R-40 acrylic adhesive of Korea S Hanwha Chemical Co., with shown in weight percent be prepared.The solution that these are different is applied on PET, cotton and the silk fabric by dip-coating, carries out drying and solidifies 3 minutes at 180 ℃ at 120 ℃.Crocking fastness is estimated with AATCC testing method 8-1996, and the K/S value uses the Hunter labMiniscan XE-Plus that as above discussed to measure.
Table 4
8 1.5 0.0 6.0 4.9 3.5 7.8 3.5 15.5 2.5
For example should be noted that the Soluryl R-40 of 6 weight percents and the Snowtex_-AK of 1.1 weight percents have given silk fabric the highest fastness, but the feel of fabric of acrylic adhesive that for example has 6 weight percents is bad.As shown in table 4, the amount of acrylate copolymer is unconspicuous to the influence of crocking fastness.But the existence of nano SiO 2 particle shows and has improved tinctorial strength do not improve crocking fastness reliably.
Prepare red pigment solution (Emacol fuchsin mixture) by the Emacol fuchsin (30%) that mixes 23.5g, Soluryl S372 pigment dispersing agent and the 277.8g water of 46.1g from Korea S Hanwha Chemical Co. from Japanese Sanyocolor.As the thin row of 5 of following tables, with shown in weight percent add Soluryl R-40 acrylic adhesive and Snowtex_-AK (in certain embodiments).Dip-coating fabric and 180 ℃ of thermal treatments 3 minutes.These results show between existence and the crocking fastness performance of amount, nano particle of acrylic adhesive significantly not related.
Table 5
Figure A20058004993800141
Has and do not have the dip-coating test of the fabric of nano particle and silane coupling agent
Be immersed in PET, cotton and silk fabric in the China ink as described in Table 6 and dry a whole night in the open.This exsiccant fabric is used the stentering machine of small test chamber scale solidified 3 minutes, in the mobile tap water, clean and drying at 180 ℃.Before immersion, add described composition and use Zr pearl grinding plant to grind 2 hours.After grinding, use Whatmann filter paper to filter (No.1 and No.5) in this mixture.
Table 6
Figure A20058004993800152
Estimate colour (K/S, L, a, b) and the color fastness of friction resistant.The results are shown in the table 7,8 and 9.
Table 7
Example 1 Example 4 Example 5
Fabric PET Cotton Silk PET Cotton Silk PET Cotton Silk
K/S (560nm) 10.25 6.11 6.93 11.27 7.21 10.52 13.62 7.41 10.69
L 38.26 44.35 41.76 36.92 42.64 38.81 35.40 43.05 38.42
A 45.31 44.16 43.16 45.01 45.87 48.66 46.30 45.94 48.12
B 7.93 8.86 5.66 9.21 11.23 9.11 10.94 11.44 10.99
Crocking fastness (doing) 2.5 3.5 3.5 3.0 3.5 3.5 3.0 3.0 3.5
Crocking fastness (doing) 1.0 3.0 3.5 1.0 3.0 3.0 2.0 3.0 3.0
Table 8
Example 2 Example 6 Example 7
Fabric PET Cotton Silk PET Cotton Silk PET Cotton Silk
K/S (560nm) 11. 7.31 10.13 9.46 7.31 11.86 10.99 8.39 10.80
L 37.67 42.88 38.88 39.24 42.43 37.64 37.85 41.56 38.68
A 45.20 47.57 48.25 45.06 45.79 48.65 45.89 47.75 48.53
B 8.47 11.17 9.28 6.48 11.35 10.76 8.46 12.89 10.40
Crocking fastness (doing) 3.0 3.0 2.5 3.5 3.0 3.0 3.0 2.5 3.0
Crocking fastness (doing) 2.0 3.0 2.0 1.5 2.5 3.5 2.0 3.0 4.0
Table 9
Example 3 Example 8 Example 9
Fabric PET Cotton Silk PET Cotton Silk PET Cotton Silk
K/S (560nm) 12.83 7.57 12.41 13.89 8.46 12.96 12.44 8.30 14.58
L 36.73 42.66 37.11 36.04 41.47 37.44 36.75 41.93 37.04
A 47.40 47.09 48.85 47.78 47.90 50.21 46.94 48.31 51.79
B 9.36 10.98 11.02 10.46 12.94 10.87 9.43 12.41 12.99
Crocking fastness 2.0 3.0 3.5 2.5 3.0 3.5 3.0 2.5 3.5
Crocking fastness 2.5 3.0 3.5 1.5 3.0 3.5 2.0 3.0 4.0
Shown in top table 7,8 and 9,, Snowtex_-AK and silane coupling agent are joined the pigment inks with polymer bonding agent system improved tinctorial strength and crocking fastness more significantly than the pigment inks that has only added the polymer bonding agent.
Has and do not have the commercially available China ink of nano particle and silane coupling agent
Four kinds of commercially available pigment inks that have and do not have Snowtex_-AK and 3-glycidoxypropyltrime,hoxysilane (GPTS) have been tested.Three kinds of different fabrics are immersed in this pigment inks batching, dry/180 ℃ of thermal treatments 3 minutes and in the mobile tap water, clean.Compare tinctorial strength and crocking fastness and display result in table 10,11,12 and 13.
Table 10
Ciba Specialty Chemical, the 100%Irgaphore PigmentBlue China ink of Inc. Irgaphore Pigment Blue China ink 18g+Snowtex_-AK 1g+GPTS 1g
Fabric PET Cotton Silk PET Cotton Silk
K/S(610nm) 3.43 4.56 11.70 16.63 8.09 13.95
L 44.13 46.66 33.50 30.69 37.82 37.02
a -8.47 -6.90 -1.47 -3.06 -4.10 -2.18
b -31.39 -30.17 -36.41 -32.60 -33.19 -34.49
Crocking fastness (doing) 3.0 3.5 3.5 3.0 3.0 3.5
Crocking fastness (wetting) 2.5 3.5 4.0 3.0 3.0 3.5
Table 11
Ciba Specialty Chemical, the 100%Irgaphore Pigment Red China ink of Inc. Irgaphore Pigment Red China ink 18g+ Snowtex_-AK 1g+GPTS 1g
Fabric PET Cotton Silk PET Cotton Silk
K/S(560nm) 5.53 3.84 11.47 13.87 7.56 10.94
L 45.40 46.88 38.45 35.60 42.69 39.45
a 40.46 38.83 47.92 45.29 46.53 49.25
b 0.34 5.55 9.25 9.06 11.98 11.12
Crocking fastness (doing) 3.0 3.0 3.0 3.5 3.0 3.5
Crocking fastness (wetting) 2.5 3.5 3.5 2.0 3.0 3.5
Table 12
Ciba Specialty Chemical, the 100%Irgaphore Pigment Yellow China ink of Inc. Irgaphore Pigment Yellow China ink 18g+Snowtex_-AK 1g+GPTS 1g
Fabric PET Cotton Silk PET Cotton Silk
K/S (400nm) 4.01 2.94 5.91 8.02 7.84 11.44
L 83.82 85.25 81.42 83.85 85.12 82.46
A -2.54 -5.14 -2.75 0.59 -2.25 0.49
B 65.91 59.36 72.81 84.39 80.77 79.57
Crocking fastness (doing) 4.0 3.5 3.5 4.5 4.5 4.5
Crocking fastness (wetting) 2.5 4.0 4.0 4.5 4.5 4.5
Table 13
Ciba Specialty Chemical, the 100%Irgaphore Pigment Black China ink of Inc. Irgaphore Pigment Black China ink 18g+ Snowtex_-AK 1g+GPTS 1g
Fabric PET Cotton Silk PET Cotton Silk
K/S (680nm) 5.76 5.35 16.68 16.19 5.37 11.16
L 34.46 34.19 20.90 23.02 32.66 25.20
A -0.03 0.37 0.91 -0.54 0.55 0.73
B -1.85 1.18 -2.99 -2.71 1.81 -1.62
Crocking fastness (doing) 2.0 3.5 4.5 4.0 3.0 3.0
Crocking fastness (wetting) 3.0 2.5 3.0 3.0 3.5 3.5
By the interpolation of Snowtex_-AK and GPTS, the pigment inks of whole four kinds of colors has shown that crocking fastness or tinctorial strength improve greatly.In silk fabric, do not find significantly to improve, but the tinctorial strength of polyester textile or crocking fastness are significantly improved.
Digital inkjet printer test with China ink of nano particle and silane coupling agent
Prepare the China ink of the digital inkjet printer that is used to have extensive format, and on polyester, cotton fabric and silk, carried out the ink-jet test.The high speed ball mill that use has 0.3mm diameter Zr pearl carried out ball milling 2 hours to this millbase composition.
The preparation of table 13 millbase
Weight of additive per-cent
Carbon Black 7 solution (15wt%) 81
Pigment Blue 15:3 solution (15wt%) 25
Pigment Yellow74(15wt%) 66.5
Pigment Red 122(15wt%) 80.2
Snowtex_-AK 5 5 5 5
Silo-Ace S-510 5 5 5 5
Soluryl R-40 5.5 5.5 5.5 5.5
Sancure AU4010 2 0 0 0
Carbosett 0 2 2 2
Surfynol DF75 1 1 1 1
Trolamine 0.5 0 0 0
Deionized water 0 57.5 57.5 1.3
The China ink batching
After the grinding, following chemical is joined make final China ink batching in the millbase of table 13.
Table 14
Weight of additive per-cent Black Blue Yellow Red
The tinting material millbase, the row composition is corresponding to table 13 same column composition 85.1 94.1 90.4 74.2
2-Pyrrolidone 8.5 3 5 10
PEG600 5.5 0 0 0
PEG400 0 0 0 10
PEG200 0 2 4 0
Glycerine 0 0 0 5
Surfynol 504 0.3 0.3 0.3 0.2
PMC Speclaltiex Group, Cobratec 99 corrosion inhibitors of Inc 0.3 0.3 0.3 0.3
The Proxel GXL biocide 9.3%1 of Zeneca AG Products Inc., 2-benzisothiazole-3-ketone (CAS # 2643-33-5) 0.3 0.3 0.3 0.3
Being used for the printing press of batching of printing table 14 is Mimaki Texitle-jet TX2-1600.There is not big problem in the China ink of printshop preparation.For this textile printing machine, nano SiO 2 particle and silane coupling agent are free from side effects to ink-jet from the ink-jet tube.Comprise CYMK (cyan, yellow, magenta, black), 8 look pigment inks with nano SiO 2 particle use same mode as shown in table 14 to be prepared.
The color fastness of pigment inks is illustrated in following table 15,16 and 17.
Table 15
Fastness result on cotton fabric
Color Clean fastness (colour-change) Light Crocking fastness
Do Wet
Cyan 4-5 4-5 4 3
Yellow 4-5 4-5 4 4
Pinkish red 4-5 4-5 4-5 3-4
Black 4-5 4-5 3-4 3
Nattierblue 4-5 4-5 4 4
Light magenta 4-5 4-5 4-5 4-5
Grey 4-5 4-5 4-5 4
Red 4-5 4-5 3 3
Table 16
Fastness result on silk fabric
Color Clean fastness (colour-change) Light Crocking fastness
Do Wet
Cyan 4-5 4-5 3 3
Yellow 4-5 4-5 4 4
Pinkish red 4-5 4-5 4 4
Black 4-5 4-5 3 3
Nattierblue 4-5 4-5 4 4-5
Light magenta 4-5 3-4 4-5 4
Grey 4-5 3-4 4-5 4-5
Red 4-5 4-5 3 3-4
Table 17
Fastness result on polyester textile
Color Clean fastness (colour-change) Light Crocking fastness
Do Wet
Cyan 3-4 4 4-5 4-5
Yellow 4-5 4 5 4-5
Pinkish red 4 4 4 3
Black 4-5 4 4-5 4
To understand as those skilled in the art, change of the present invention and change are considered to be in those skilled in the art's the limit of power.The example of such change is comprised in the patent described above, and they each all is incorporated herein by reference with it with the degree that is consistent with this specification sheets.Inventor's purpose is that these changes and change are fallen within the scope of the present invention.

Claims (14)

1. printing composition, it comprises water, China ink, caking agent, nano SiO 2 particle and silane coupling agent.
2. the composition of claim 1, the ratio of wherein said nano particle and coupling agent is 3: 1-1: 3.
3. the composition of claim 2, the amount of wherein said nano particle is the 0.1-10 weight percent.
4. the composition of claim 1, the amount of wherein said caking agent is about 0.1-10 weight percent.
5. the composition of claim 1, it further comprises dispersion agent.
6. the composition of claim 1, wherein said silane coupling agent is selected from vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl dimethyl dichlorosilane (DMCS), the vinyl methyl dimethoxysilane, the vinyl methyldiethoxysilane, 5-hexenyl Trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-(methyl) acryloxy propyl group methyldiethoxysilane, 4-ethenylphenyl Trimethoxy silane, 3-(4-ethenylphenyl) propyl trimethoxy silicane, 4-ethenylphenyl methyltrimethoxy silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-(2-amino-ethyl) TSL 8330, the 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercapto propyl group methyl dimethoxysilane, 3-mercapto propyl group methyldiethoxysilane, and their mixture and partial hydrolysate.
7. the composition of claim 1, wherein said nano particle have the metal ion that is selected from aluminium, copper, nickel, silver, gold and composition thereof.
8. the composition of claim 1, said composition are printed on the ground of laminating material of the compound fabric, nonwoven fabric, melt-blown web, yarn fabric and spunbond and the melt-blown web that are selected from water acupuncture manipulation slurry and spun-bonded fibre.
9. the composition of claim 8, wherein said ground is the yarn fabric of being made by cotton, silk, polyester or nylon.
10. printed fabric that has the dried residue of the composition that water-based uses thereon, wherein said composition comprises the nano particle of 0.1-10 weight percent, the silane coupling agent of 0.1-10 weight percent, the caking agent and the China ink of 0.1-10 weight percent.
11. the printed fabric of claim 10, wherein said silane coupling agent are selected from 3-glycidoxypropyltrime,hoxysilane and 3-aminopropyltriethoxywerene werene and composition thereof.
12. the printed fabric of claim 10, this fabric are selected from the laminating material of compound fabric, nonwoven fabric, melt-blown web, yarn fabric and spunbond and the melt-blown web of water acupuncture manipulation slurry and spun-bonded fibre.
13. the printed fabric of claim 10, wherein, before drying, by be selected from slit mouth mould, directly intaglio printing, have that offset printing intaglio printing, curtain coating, the slip that contrary roller shifts is coated with, front and back roller coat, extrusion coated, roto-sifter, nozzle are used, flexographic typography, rod are coated with, air knife blade coating, blade coating, scraper coating, dip-coating subsequently the method for extrusion roll, spin coating, damping coating, brushing described composition is administered on the described fabric.
14. a method of making the fabric of printing, it comprises step:
With 1: 3-3: 1 ratio is mixed nano SiO 2 particle and silane coupling agent,
To wherein adding entry, caking agent and pigment,
Being ground to particle size is that 150-200nm makes abrasive composition,
Use described composition to described fabric; With
Dry described fabric.
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