CN107284068B - Water-based ink is indoors and the method for outdoor inkjet printing design for advertisement - Google Patents

Water-based ink is indoors and the method for outdoor inkjet printing design for advertisement Download PDF

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Publication number
CN107284068B
CN107284068B CN201710521384.5A CN201710521384A CN107284068B CN 107284068 B CN107284068 B CN 107284068B CN 201710521384 A CN201710521384 A CN 201710521384A CN 107284068 B CN107284068 B CN 107284068B
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water
grams
ink
microlith
block copolymer
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CN107284068A (en
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孙铁宁
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孙铁宁
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023Digital printing methods characterised by the inks used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041Digital printing on surfaces other than ordinary paper
    • B41M5/0047Digital printing on surfaces other than ordinary paper by ink-jet printing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • C09D5/024Emulsion paints including aerosols characterised by the additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a kind of water-based inks indoors and the method for outdoor inkjet printing design for advertisement, comprising the following steps: (1) provide substrate, the substrate is advertising cloth and/or poster paper;(2) water paint is coated at least one surface of the substrate;(3) by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, to obtain design for advertisement.Method this method of the invention is not simply, conveniently, affected by environment, environmentally protective without using the solvent-based inks of high pollution, and the ink pattern has the characteristics that weather resistance is good, waterproof performance is strong and high abrasion, excellent combination property.

Description

Water-based ink is indoors and the method for outdoor inkjet printing design for advertisement
Technical field
The invention belongs to inkjet printing technology field, more particularly it relates to which a kind of water-based ink is indoors and family The method of outer inkjet printing design for advertisement.
Background technique
With the development of interior decoration industry and advertising sector, ink-jet technology is widely used.Such as indoors And the market demand of outdoor inkjet printing design for advertisement is increasing, can see, be beaten extensively in daily life by ink-jet It is imprinted on the product that substrate surface shows various exquisite patterns.
The ink used in ink-jet technology has water-based ink and two kinds of oil-based ink.The properties of product of oil-based ink are preferable, but due to Using poisonous and hazardous organic solvent, environmental pollution is serious, and the feature of environmental protection is poor, largely effects on its use scope.Water-based ink is cheap, pacifies Entirely, text or picture clarity height, organic solvent-resistant pollution-free, formed, thus become the major demands of future market.But It is that the outstanding problem of water-based ink is that the text being sprayed into or image waterfastness performance, weather resistance and wearability are bad, therefore It is difficult to obtain the ink-jet products of excellent combination property.
On the matrixes such as paper, usually there is polymer coating, is capable of fixing the ink sprayed or dyestuff on matrix.In order to mention The water-fast property of high dyestuff, USP 5250107 propose ink composition in be added the polymer salt containing ammonium, zirconium, increase dyestuff with Hydrogen bond between matrix;USP 6106598 proposes that silica gel colloid is added in ink;The it is proposed of USP 6224660 is added siliceous in ink Organic polymer;USP 6001899, which proposes to be added, forms sat linkage etc. containing quaternary ammonium salt cationic polymer and anionic dye.But It is that the above method cannot solve the problems, such as the water-fast, weather-proof and wear-resisting of water-based ink simultaneously.In addition, at abroad, usually substantially Face ink jet printer requires to use under conditions of certain temperature (such as 15-30 DEG C), humidity (such as relative humidity 35-60%).But China Geographical environment and condition differ greatly, and the especially Shelter in South China Cities summer humidity such as Changsha, Wuhan, Guangzhou, Nanchang is up to 90%, temperature Often at 36 DEG C or more.In addition, the domestic spray painted paper in China and overlay film coating quality index are sometimes up to the purpose less than fixed dye, from And the dye image for forming air brushing gradually generates dyestuff and vacillates after printing (3-30 days), especially domestic and international common dyestuff Such as weld C.I. acid yellow 23, C.I. directly Huang 132 and part orchil image as caused by C.I. acid red 53 It is serious for vacillating, and yellow and red text or image sharpness is caused to reduce.Simultaneously, there is also solvents for solvent inkjet ink at present Volatilization causes environment very severe, Air seriously polluted and the three major issues such as substrate PVC is non-degradable, it would be highly desirable to solve.
Hence it is highly desirable to carry out the improvement of formula and technique, a kind of water-based ink is provided indoors and outdoor ink-jet The method of print ad pattern, this method is not simply, conveniently, (temperature and humidity) affected by environment, and can prepare while have There is the design for advertisement of high durable, high waterproof and high-wear resistance.
Summary of the invention
To solve the above-mentioned problems, one aspect of the present invention provides a kind of water-based ink indoors and outdoor inkjet printing The method of design for advertisement, comprising the following steps:
(1) substrate is provided, the substrate is advertising cloth and/or poster paper;
(2) water paint is coated at least one surface of the substrate;
(3) by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, to obtain advertisement figure Sample.
In one embodiment, the water paint, in parts by weight, preparing raw material includes following components:
Preferably, the water paint, in parts by weight, preparing raw material includes following components:
In one embodiment, the water paint, in parts by weight, preparing raw material also includes: 3-8 parts of sulfonation Polyetheramine-sulfonated polyethersulfone block copolymer;Preferably, the sulfonated polyether amine-sulfonated polyethersulfone block copolymer is 5 parts.
In one embodiment, the water-based ink, in parts by weight, preparing raw material includes following components:
Preferably, the water-based ink, in parts by weight, preparing raw material includes following components:
In one embodiment, the water-based ink, in parts by weight, preparing raw material also includes: 1-5 parts of poly- season Ammonium salt-polybenzimidazoles block copolymer;Preferably, the polyquaternium-polybenzimidazoles block copolymer is 3 parts.
In one embodiment, it is black to be selected from black (MICROLITH:Black) C-WA of micro- high-tensile strength, micro- high-tensile strength for the pigment (MICROLITH:Black) red (MICROLITH:Red) B-WA of C-K, carbon black, micro- high-tensile strength, micro- high-tensile strength are red (MICROLITH:Red) 4C-K, micro- high-tensile strength indigo plant (MICROLITH:Blue) 4G-WA, micro- high-tensile strength indigo plant (MICROLITH:Blue) A3R-K, micro- high-tensile strength are yellow (MICROLITH:Yellow) at least one of BAW-WA and micro- high-tensile strength Huang (MICROLITH:Yellow) 3R-K.
In one embodiment, the pigment dispersing agent is sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M- The mixture that the weight ratio of C is 0.6-0.9: 1;Preferably, the weight of sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C Measure ratio 0.7: 1.
In one embodiment, other described auxiliary agents are TW-20 and/or QPE-20.
In one embodiment, the moisturizer is selected from glycerol, ethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol (DEG), three At least one of glycol and sorbierite.
In one embodiment, the surfactant is fluoro-alkyl alkoxide compound (Fluorad Fc171) Or fluoroalkyl (Fluorad Fc430).
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understand Open content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise.
In some examples, approximate term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and In claims, range restriction can be combined and/or be exchanged, these ranges if not stated otherwise include contained therebetween All subranges.
One aspect of the present invention provides a kind of water-based ink indoors and the method for outdoor inkjet printing design for advertisement, packet Include following steps:
(1) substrate is provided, the substrate is advertising cloth and/or poster paper;
(2) water paint is coated at least one surface of the substrate;
(3) by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, to obtain advertisement figure Sample.
Water paint
Water paint for the application is not particularly limited, and be can be commercialized product or is synthesized by experiment It arrives.Such as the water paint, in parts by weight, preparing raw material includes following components:
Preferably, the water paint, in parts by weight, preparing raw material includes following components:
For further improving performance, the water paint, in parts by weight, preparing raw material also includes: 3-8 parts Sulfonated polyether amine-sulfonated polyethersulfone block copolymer;Preferably, the sulfonated polyether amine-sulfonated polyethersulfone block copolymer is 5 Part.
In one embodiment, the method for the sulfonated polyether amine-sulfonated polyethersulfone block copolymer includes following step It is rapid:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer.
In one embodiment, above-mentioned water paint the preparation method comprises the following steps:
The material component is added in blender and is sufficiently mixed after twenty minutes, discharging obtains.
Water-based ink
Water paint for the application is not particularly limited, and be can be commercialized product or is synthesized by experiment It arrives.Such as the water paint, in parts by weight, preparing raw material includes following components:
It includes following components that it, which prepares raw material:
Preferably, the water-based ink, in parts by weight, preparing raw material includes following components:
It is highly preferred that the water-based ink, in parts by weight, preparing raw material includes following components:
For further improving performance, the water-based ink, in parts by weight, preparing raw material also includes: 1-5 parts Polyquaternium-polybenzimidazoles block copolymer;Preferably, the polyquaternium-polybenzimidazoles block copolymer is 3 parts.
In one embodiment, the polyquaternium-polybenzimidazoles block copolymer preparation method includes following Step:
(1) polyquaternium prepolymer is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.097mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium Prepolymer;
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flask, connection nitrogen inlet, drying tube, nitrogen outlet and machinery Blender.It is being passed through nitrogen after five minutes, 3, the 3'- diaminobenzidine (DAB) of 0.01mol is being added in three-neck flask, to DAB is uniformly dispersed be dissolved in polyphosphoric acids after, add 0.009mmol terephthalic acid (TPA), later be added 20mmol P2O5 Water for generating in absorbing reaction opens mechanical stirring and heats up simultaneously, keeps 200 DEG C of reaction 20h.It is cold to temperature of reaction system But it to after 150 DEG C, pours into deionized water and precipitates, repeatedly washing removal polyphosphoric acids.With the hydrogen-oxygen of a large amount of mass fractions 10% Change sodium water solution agitator treating 24 hours and neutralize remaining phosphoric acid, then washs repeatedly removal sodium hydroxide repeatedly with deionization.It will Gained is deposited in vacuum drying oven at 60 DEG C and dries to get polybenzimidazoles prepolymer;
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In 1000ml dry three-necked bottle, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added (2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide and 2 grams of sodium carbonate obtain after reacting 5 hours at 60 DEG C Clear yellow viscous solution, is cooled to room temperature, and pours into deionized water and precipitates, and is washed with deionization repeatedly to neutrality, is then taken out repeatedly Filter, collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyquaternium-polybenzimidazoles block copolymer.
It is preferably carried out in mode in one kind, above-mentioned water paint, in parts by weight, preparing raw material also includes: 5 parts Sulfonated polyether ketone modified graphene oxide, and the sulfonated polyether ketone modified graphene oxide the preparation method comprises the following steps:
In 1000mL dry three-necked bottle, the sulfonation 4 of 0.0106mol is weighed respectively, 4'- difluoro benzophenone, 0.01mol grams of 4,4'- '-biphenyl diphenol is dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, adds the carbonic acid of 0.03mol The toluene of sodium and 20mL leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room Temperature after the para-aminophenol of 0.0006mol is added, leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response After 12 hours, be down to room temperature, obtain dark brown viscous liquid, then into this reaction system be added 30 grams of graphene oxides and 5 grams of KH-560 lead to nitrogen protection after 1 hour, heat up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly 2000mL go from In sub- water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, is dried in vacuum In case, 50 DEG C drying 24 hours, obtain sulfonated polyether ketone modified graphene oxide.
In one embodiment, above-mentioned water-based ink the preparation method comprises the following steps:
The material component is added in blender after being sufficiently mixed 30 minutes, discharging obtains.
Pigment
Pigment for the application is not particularly limited, and be can be commercialized product or is obtained by testing synthesis. In one embodiment, it is black to be selected from black (MICROLITH:Black) C-WA of micro- high-tensile strength, micro- high-tensile strength for the pigment (MICROLITH:Black) red (MICROLITH:Red) B-WA of C-K, carbon black, micro- high-tensile strength, micro- high-tensile strength are red (MICROLITH:Red) 4C-K, micro- high-tensile strength indigo plant (MICROLITH:Blue) 4G-WA, micro- high-tensile strength indigo plant (MICROLITH:Blue) A3R-K, micro- high-tensile strength are yellow (MICROLITH:Yellow) at least one of BAW-WA and micro- high-tensile strength Huang (MICROLITH:Yellow) 3R-K.
Pigment dispersing agent
Pigment dispersing agent for the application is not particularly limited, and can be commercialized product or by experiment synthesis It obtains.In one embodiment, the pigment dispersing agent is sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C The mixture that weight ratio is 0.6-0.9: 1;Preferably, the weight of sodium naphthalene sulfonate condensation product (Ionet D-2) and dispersant A M-C Than 0.7: 1.
Other auxiliary agents
Other auxiliary agents for the application are not particularly limited, and be can be commercialized product or are synthesized by experiment It arrives.In one embodiment, the auxiliary agent is TW-20 and/or QPE-20.
Moisturizer
Moisturizer for the application is not particularly limited, and be can be commercialized product or is synthesized by experiment It arrives.In one embodiment, the moisturizer be selected from glycerol, ethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol (DEG), triethylene glycol with And at least one of sorbierite.
Surfactant
In one embodiment, the surfactant is fluoro-alkyl alkoxide compound (Fluorad Fc171) Or fluoroalkyl (Fluorad Fc430).
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, and number used in following material is weight Part.
Embodiment 1
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 5 grams of hydroxyethyl cellulose, 10 grams of acrylic emulsion, 0.1 gram of alkyl phenol polyoxyethylene ether, 3 grams of second Glycol, 1 gram of methyl-silicone oil, 5 grams of butyl and 100 grams of deionized water, which are added in blender, is sufficiently mixed 20 After minute, discharging is obtained;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 1 gram of micro- high-tensile strength, 1 gram of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.6: 1), 10 grams of glycerol, 1 gram of TW-20,0.001 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 2
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 10 grams of hydroxyethyl cellulose, 30 grams of acrylic emulsion, 2 grams of alkyl phenol polyoxyethylene ether, 10 grams of second Glycol, 5 grams of methyl-silicone oil, 10 grams of butyl and 100 grams of deionized water, which are added in blender, to be sufficiently mixed After twenty minutes, discharging obtains;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 10 grams of micro- high-tensile strength, 10 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.6: 1), 30 grams of glycerol, 5 grams of TW-20,0.05 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 3
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl and 100 grams of deionized water, which are added in blender, is sufficiently mixed 20 After minute, discharging is obtained;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.6: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 4
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl and 100 grams of deionized water, which are added in blender, is sufficiently mixed 20 After minute, discharging is obtained;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 5
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 3 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 6
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 8 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 7
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171) and 100 grams deionized water be added blender in be sufficiently mixed After 30 minutes, discharging is obtained.
Embodiment 8
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171), 1 gram of polyquaternium-polybenzimidazoles block copolymer and After being sufficiently mixed 30 minutes in 100 grams of deionized water addition blender, discharging is obtained;
The polyquaternium-polybenzimidazoles block copolymer the preparation method comprises the following steps:
(1) polyquaternium prepolymer is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.097mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium Prepolymer;
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flask, connection nitrogen inlet, drying tube, nitrogen outlet and machinery Blender.It is being passed through nitrogen after five minutes, 3, the 3'- diaminobenzidine (DAB) of 0.01mol is being added in three-neck flask, to DAB is uniformly dispersed be dissolved in polyphosphoric acids after, add 0.009mmol terephthalic acid (TPA), later be added 20mmol P2O5 Water for generating in absorbing reaction opens mechanical stirring and heats up simultaneously, keeps 200 DEG C of reaction 20h.It is cold to temperature of reaction system But it to after 150 DEG C, pours into deionized water and precipitates, repeatedly washing removal polyphosphoric acids.With the hydrogen-oxygen of a large amount of mass fractions 10% Change sodium water solution agitator treating 24 hours and neutralize remaining phosphoric acid, then washs repeatedly removal sodium hydroxide repeatedly with deionization.It will Gained is deposited in vacuum drying oven at 60 DEG C and dries to get polybenzimidazoles prepolymer;
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In 1000ml dry three-necked bottle, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added (2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide and 2 grams of sodium carbonate obtain after reacting 5 hours at 60 DEG C Clear yellow viscous solution, is cooled to room temperature, and pours into deionized water and precipitates, and is washed with deionization repeatedly to neutrality, is then taken out repeatedly Filter, collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 9
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171), 5 grams of polyquaternium-polybenzimidazoles block copolymer and After being sufficiently mixed 30 minutes in 100 grams of deionized water addition blender, discharging is obtained;
The polyquaternium-polybenzimidazoles block copolymer the preparation method comprises the following steps:
(1) polyquaternium prepolymer is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.097mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium Prepolymer;
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flask, connection nitrogen inlet, drying tube, nitrogen outlet and machinery Blender.It is being passed through nitrogen after five minutes, 3, the 3'- diaminobenzidine (DAB) of 0.01mol is being added in three-neck flask, to DAB is uniformly dispersed be dissolved in polyphosphoric acids after, add 0.009mmol terephthalic acid (TPA), 20mmol be added later Water of the P2O5 for generating in absorbing reaction opens mechanical stirring and heats up simultaneously, keeps 200 DEG C of reaction 20h.To reaction system temperature It after degree is cooled to 150 DEG C, pours into deionized water and precipitates, repeatedly washing removal polyphosphoric acids.With a large amount of mass fractions 10% Remaining phosphoric acid is neutralized within sodium hydrate aqueous solution agitator treating 24 hours, then washs repeatedly removal hydroxide repeatedly with deionization Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and is dried to get polybenzimidazoles prepolymer;
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In 1000ml dry three-necked bottle, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added (2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide and 2 grams of sodium carbonate obtain after reacting 5 hours at 60 DEG C Clear yellow viscous solution, is cooled to room temperature, and pours into deionized water and precipitates, and is washed with deionization repeatedly to neutrality, is then taken out repeatedly Filter, collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 10
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171), 3 grams of polyquaternium-polybenzimidazoles block copolymer and After being sufficiently mixed 30 minutes in 100 grams of deionized water addition blender, discharging is obtained;
The polyquaternium-polybenzimidazoles block copolymer the preparation method comprises the following steps:
(1) polyquaternium prepolymer is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.097mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium Prepolymer;
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flask, connection nitrogen inlet, drying tube, nitrogen outlet and machinery Blender.It is being passed through nitrogen after five minutes, 3, the 3'- diaminobenzidine (DAB) of 0.01mol is being added in three-neck flask, to DAB is uniformly dispersed be dissolved in polyphosphoric acids after, add 0.009mmol terephthalic acid (TPA), 20mmol be added later Water of the P2O5 for generating in absorbing reaction opens mechanical stirring and heats up simultaneously, keeps 200 DEG C of reaction 20h.To reaction system temperature It after degree is cooled to 150 DEG C, pours into deionized water and precipitates, repeatedly washing removal polyphosphoric acids.With a large amount of mass fractions 10% Remaining phosphoric acid is neutralized within sodium hydrate aqueous solution agitator treating 24 hours, then washs repeatedly removal hydroxide repeatedly with deionization Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and is dried to get polybenzimidazoles prepolymer;
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In 1000ml dry three-necked bottle, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added (2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide and 2 grams of sodium carbonate obtain after reacting 5 hours at 60 DEG C Clear yellow viscous solution, is cooled to room temperature, and pours into deionized water and precipitates, and is washed with deionization repeatedly to neutrality, is then taken out repeatedly Filter, collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyquaternium-polybenzimidazoles block copolymer.
Embodiment 11
Water paint coating liquid is sprayed on to the surface of advertising cloth with the method for spraying, with roll shaft by advertising cloth surface covering Roll it is even roll reality, dried in baking oven, drying temperature be 80 degrees Celsius, drying time be 50 minutes;
With ink jet printer by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, with obtain Design for advertisement;
The water paint the preparation method comprises the following steps:
By 6 grams of hydroxyethyl cellulose, 15 grams of acrylic emulsion, 0.5 gram of alkyl phenol polyoxyethylene ether, 8 grams of second Glycol, 3 grams of methyl-silicone oil, 7 grams of butyl, 5 grams of sulfonated polyether amine-sulfonated polyethersulfone block copolymer be with And 100 grams deionized water be added blender in be sufficiently mixed after twenty minutes, discharging obtains, wherein sulfonated polyether amine-sulphur Change polyethersulfone block copolymer the preparation method comprises the following steps:
(1) preparation of polyetheramine prepolymer
In 1000mL dry three-necked bottle, 100 grams of octafluorobiphenyl diglycidyl ether (epoxide number is sequentially added 0.45mol/100g), the benzylamine of 0.22mol and 700 grams of dimethyl sulfoxides lead to nitrogen protection and magnetic agitation;1h is stirred at room temperature Afterwards, it heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, obtain epoxy-capped polyetheramine pre-polymer solution;
(2) polyetheramine-sulfonated polyethersulfone block copolymer preparation
In the 1000mL dry three-necked bottle, weigh respectively 0.0105mol sulfonation dichloro diphenyl sulfone, 0.01mol grams 4,4'- '-biphenyl diphenols are dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, add the sodium carbonate of 0.03mol and the first of 20mL Benzene leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room temperature, be added After the para-aminophenol of 0.0005mol, lead to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 12 hours Afterwards, it is down to room temperature, obtains dark brown viscous liquid, the epoxy-capped polyetheramine prepolymer for then obtaining above-mentioned steps (1) is molten This reaction system is all added in liquid, leads to nitrogen protection after 1 hour, heats up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly In 2000mL deionized water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, filters and collect polymerization Object, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyetheramine-sulfonated polyethersulfone block copolymer;
(3) sulfonated polyether amine-sulfonated polyethersulfone block copolymer preparation
Polyetheramine-sulfonated polyethersulfone block copolymer 1 gram obtained by step (2) is taken, the dense sulphur of mass fraction 98% is dissolved in It in acid, after being reacted 5 hours under ice bath, pours into ice water, after washing the product repeatedly with ice water, filters simultaneously collected polymer, in In vacuum drying oven, 50 DEG C drying 24 hours, obtain sulfonated polyether amine-sulfonated polyethersulfone block copolymer;
The water-based ink the preparation method comprises the following steps:
By black (MICROLITH:Black) C-WA of 3 grams of micro- high-tensile strength, 3 grams of pigment dispersing agent (sodium naphthalene sulfonate condensation product The mixture that the weight ratio of (Ionet D-2) and dispersant A M-C are 0.7: 1), 20 grams of glycerol, 3 grams of TW-20,0.02 gram Fluoro-alkyl alkoxide compound (Fluorad Fc171), 3 grams of polyquaternium-polybenzimidazoles block copolymer, 5 grams Sulfonated polyether ketone modified graphene oxide and 100 grams deionized water be added blender in be sufficiently mixed 30 minutes after, out Material obtains;
The polyquaternium-polybenzimidazoles block copolymer the preparation method comprises the following steps:
(1) polyquaternium prepolymer is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.097mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium Prepolymer;
(2) polybenzimidazoles prepolymer is prepared
180g polyphosphoric acids is placed in 250ml three-neck flask, connection nitrogen inlet, drying tube, nitrogen outlet and machinery Blender.It is being passed through nitrogen after five minutes, 3, the 3'- diaminobenzidine (DAB) of 0.01mol is being added in three-neck flask, to DAB is uniformly dispersed be dissolved in polyphosphoric acids after, add 0.009mmol terephthalic acid (TPA), 20mmol be added later Water of the P2O5 for generating in absorbing reaction opens mechanical stirring and heats up simultaneously, keeps 200 DEG C of reaction 20h.To reaction system temperature It after degree is cooled to 150 DEG C, pours into deionized water and precipitates, repeatedly washing removal polyphosphoric acids.With a large amount of mass fractions 10% Remaining phosphoric acid is neutralized within sodium hydrate aqueous solution agitator treating 24 hours, then washs repeatedly removal hydroxide repeatedly with deionization Sodium.Gained is deposited in vacuum drying oven at 60 DEG C and is dried to get polybenzimidazoles prepolymer;
(3) polyquaternium-polybenzimidazoles block copolymer is prepared
In 1000ml dry three-necked bottle, polyquaternium prepolymer, 1 gram of step obtained by 1 gram of step (1) are sequentially added (2) gained polybenzimidazoles prepolymer, 100ml dimethyl sulfoxide and 2 grams of sodium carbonate obtain after reacting 5 hours at 60 DEG C Clear yellow viscous solution, is cooled to room temperature, and pours into deionized water and precipitates, and is washed with deionization repeatedly to neutrality, is then taken out repeatedly Filter, collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain polyquaternium-polybenzimidazoles block copolymer;
The sulfonated polyether ketone modified graphene oxide the preparation method comprises the following steps:
In 1000mL dry three-necked bottle, the sulfonation 4 of 0.0106mol is weighed respectively, 4'- difluoro benzophenone, 0.01mol grams of 4,4'- '-biphenyl diphenol is dissolved in the N-Methyl pyrrolidone (NMP) of 50mL, adds the carbonic acid of 0.03mol The toluene of sodium and 20mL leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response 24 hours, be then down to room Temperature after the para-aminophenol of 0.0006mol is added, leads to nitrogen protection after 1 hour, by reaction system at 180 DEG C sustained response After 12 hours, be down to room temperature, obtain dark brown viscous liquid, then into this reaction system be added 30 grams of graphene oxides and 5 grams of KH-560 lead to nitrogen protection after 1 hour, heat up 80 DEG C after reacting 4 hours, reaction solution is poured into rapidly 2000mL go from In sub- water, a large amount of solid precipitatings are obtained;After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, is dried in vacuum In case, 50 DEG C drying 24 hours, obtain sulfonated polyether ketone modified graphene oxide.
Test method
Weatherability test:
Cause weatherability to reduce the ozone in mainly daylight middle-ultraviolet lamp and atmosphere, proposes easy solarization jail accordingly Spend test method and ozone proof test method.Through repetition test gradual perfection test process.Using the principle of color difference to the party Method has added quantitative assessment, sets up connection between color difference and light fastness rank and resistance to ozone level by analyzing, can be with The rank of light fastness, resistance to ozone level are extrapolated by attenuation rate or value of chromatism Δ E, it is simple and fast.With optics scenograph Eye-one test case 1, example 2, example 3, example 4, example 5 print the color density of color lump, then under uv lamps according to 3 hours, Its color density is being tested, color density attenuation rate of the color lump before and after UV lamp irradiation is calculated.Color density attenuation rate is bigger, shows sun-proof Property is poorer.On the contrary, color density attenuation rate is lower, light resistance is better.
The color density of color lump is printed with optics scenograph Eye-one test case 1, example 2, example 3, example 4, example 5, Then its color density is being tested in (ozone disinfection cabinet) 3 hours under ozone environment, calculates color lump before and after ozone disinfection cabinet storage Color density attenuation rate.Color density attenuation rate is bigger, shows that resistance to ozone is poorer.On the contrary, color density attenuation rate is lower, resistance to ozone is got over It is good.
Attenuation rate=(color density after original color density-test)/original color density
Water resistance detection:
Detection method: intercepting one section of advertising cloth of inkjet printing, impregnate in 50 DEG C of deionized water, and observation ink fades And diffusion time, and record.Dipping for 24 hours after, take out spontaneously dry, and with untreated samples ready visual contrast.
The detection of salt tolerant acidity:
Detection method: intercepting one section of advertising cloth of inkjet printing, impregnates for 24 hours in 10% (volume ratio) aqueous hydrochloric acid solution Afterwards, impregnate 10min in deionized water, take out and spontaneously dry, and with untreated samples ready visual contrast.
Resistance to alcohol repellency detection:
Detection method: intercepting one section of advertising cloth of inkjet printing, impregnates 20min in 50% (volume ratio) ethanol water Afterwards, take out spontaneously dry, and with untreated samples ready visual contrast.
The aqueous detection of resistant to ammonia:
Detection method: intercepting one section of advertising cloth of inkjet printing, impregnates for 24 hours in 10% (mass percent) ammonia spirit Afterwards, impregnate 20min in deionized water, take out and spontaneously dry, and with untreated samples ready visual contrast.
The heat-resisting quantity of ink detects:
Detection method: intercepting one section of advertising cloth of inkjet printing, be placed in the 100 DEG C of boiled water boiled, after dipping boils 10min Take out, spontaneously dry, and with untreated samples ready visual contrast.
The detection of ink lower temperature resistance:
Detection method: tested ink pours into cold-resistant Packaging Bottle, is put into (- 20 ± 1) DEG C cryostat to taking afterwards for 24 hours Out, after being restored to room temperature, its print performance is detected.
The wearability of ink detects:
Detection method: it is rubbed on pattern same number with coin, until there is a kind of writing abrasion mark occur, record rubs Wipe number.With the strength generally scratched, scratch the angle on 45 degree of coin and word surface back and forth on the surface of word, until there is one kind Writing surface occurs scratching trace, and record scratches number, determines wearability.
Test result is shown in Table 1.
Table 1
Above data, which can be seen that, to be compared with the traditional method, and is had using the ink-jet pattern that the method for the present invention obtains obvious Better performance thus provides advantageous effects of the invention.

Claims (8)

1. water-based ink is indoors and the method for outdoor inkjet printing design for advertisement, which comprises the following steps:
(1) substrate is provided, the substrate is advertising cloth and/or poster paper;
(2) water paint is coated at least one surface of the substrate;
(3) by water-based ink inkjet printing on the water-borne coating of step (2) resulting substrate, to obtain design for advertisement;
The water paint, in parts by weight, preparing raw material includes following components:
The water paint, in parts by weight, preparing raw material also includes: 3-8 parts of sulfonated polyether amine-sulfonated polyethersulfone block Copolymer.
2. the method according to claim 1, wherein the water-based ink prepares raw material packet in parts by weight Containing following components:
3. according to the method described in claim 2, it is characterized in that, the water-based ink prepares raw material also in parts by weight Include: 1-5 parts of polyquaternium-polybenzimidazoles block copolymer.
4. according to the method described in claim 2, it is characterized in that, the pigment be selected from micro- high-tensile strength it is black (MICROLITH: Black) black (MICROLITH:Black) C-K of C-WA, micro- high-tensile strength, carbon black, red (MICROLITH:Red) B-WA of micro- high-tensile strength, micro- high Red (MICROLITH:Red) 4C-K of power, micro- high-tensile strength indigo plant (MICROLITH:Blue) 4G-WA, micro- high-tensile strength it is blue (MICROLITH: Blue) A3R-K, micro- high-tensile strength Huang (MICROLITH:Yellow) BAW-WA and micro- high-tensile strength Huang (MICROLITH:Yellow) 3R-K At least one of.
5. according to the method described in claim 2, it is characterized in that, the pigment dispersing agent is sodium naphthalene sulfonate condensation product and dispersion The mixture that the weight ratio of agent AM-C is 0.6-0.9: 1, wherein the sodium naphthalene sulfonate condensation product is Ionet D-2.
6. according to the method described in claim 2, it is characterized in that, other auxiliary agents are TW-20 and/or QPE-20.
7. according to the method described in claim 2, it is characterized in that, the moisturizer is selected from glycerol, ethylene glycol, propylene glycol, gathers At least one of ethylene glycol, diethylene glycol (DEG), triethylene glycol and sorbierite.
8. according to the method described in claim 2, it is characterized in that, the surfactant is fluoro-alkyl alkoxide compound Or fluoroalkyl, wherein the fluoro-alkyl alkoxide compound is Fluorad Fc171, and the fluoroalkyl is Fluorad Fc430。
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