CN105463882B - A kind of gold stamping slurry and preparation method thereof - Google Patents

A kind of gold stamping slurry and preparation method thereof Download PDF

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Publication number
CN105463882B
CN105463882B CN201511027842.7A CN201511027842A CN105463882B CN 105463882 B CN105463882 B CN 105463882B CN 201511027842 A CN201511027842 A CN 201511027842A CN 105463882 B CN105463882 B CN 105463882B
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parts
gold stamping
monomer
stamping slurry
acrylic
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CN105463882A (en
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卢开平
陈任
卢杰宏
苏飞洞
卢浩标
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DONGGUAN CHANGLIAN NEW MATERIALS TECHNOLOGY Co Ltd
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DONGGUAN CHANGLIAN NEW MATERIALS TECHNOLOGY Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General 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
    • D06P1/44—General 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
    • D06P1/52—General 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 using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General 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
    • D06P1/44—General 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
    • D06P1/52—General 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 using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5271—Polyesters; Polycarbonates; Alkyd resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General 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
    • D06P1/44—General 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
    • D06P1/52—General 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 using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General 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
    • D06P1/44—General 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
    • D06P1/52—General 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 using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a kind of gold stamping slurry and preparation method thereof, and the gold stamping slurry is by the acrylic emulsion that parts by weight sum is 100 parts, and thermal fusing powder, curing agent, thickener and defoamer are prepared；Acrylic emulsion is mainly prepared by the following raw material in parts by weight：0.8~1.8 part of emulsifying agent；60~70 parts of soft monomer；20~35 parts of hard monomer；0.5~3 part of cross-linking monomer；3~5 parts of function monomer；0.15~0.4 part of initiator；0.3~1.4 part of nertralizer；0.3~0.5 part of pH buffer；0~2.4 part of adipic dihydrazide；88~115 parts of deionized water.The gold stamping slurry can be as the sticker between orange cold foil and any cloth, it is easy to operate that it makes stamp process, stamp is not tacky and blocking point is low, there is superelevation wash durability with its manufactured printing textile, mirror effect and soft is not lost, and there is good application prospect in weaving and paper product field.

Description

A kind of gold stamping slurry and preparation method thereof
Technical field
The invention belongs to printing technique field, more particularly to a kind of gold stamping slurry and preparation method thereof.
Background technology
Gold stamping stamp because its is beautiful in colour, the advantages that glittering and obtain the favor of textile industry, but yet simultaneously In the presence of many problems, washing fastness, environmental protection, flatness, pliability, high-temperature discoloration etc. are concentrated mainly on.
Solving washing fastness at present has main following several method：Glittering powder is added in gold stamping slurry, using thermal fusing powder With use chloride emulsion or chloride auxiliary agent.
CN 1769069A disclose a kind of washable, soft, glittering costume bronzing technique, and the technique mainly includes：Print Gold stamping slurry, naturally dry, hot pressing are gold stamping, high temperature bakes, and it adds 5-20% glittering powder in the soft gold stamping slurry of printing and used In bottoming；High-strength adhesion strength is gold stamping to starch for capping；Bake and rear cold tear golden paper.The patent employs glittering powder, its object is to Glittering powder is carried after gold stamping slurry film forming, orange cold foil is filled up and drops part, but because the addition of glittering powder can influence film forming matter Flatness, and then influence mirror effect.
CN 102718921A disclose a kind of Adhesive emulsion for environment-friendlytextile textile gilding printing paste and its preparation side Method, the emulsion are made up of the component of following weight percentage：Emulsifying agent 0.5%~3%, soft monomer 30%~50% are hard single Body 6%~15%, functional monomer 2%~5%, initiator 0.1%~0.3%, deionized water 40%~60%, nertralizer 0.5%~2%.Its feature can be prepared by gold stamping stamp without high temperature thermoprint, solve the problems, such as high-temperature discoloration, but its emulsion is not , can be relatively poor in terms of wash water fastness using means such as any cross-linking system or thermal fusing powders.
CN 103255646B disclose a kind of gold stamping slurry and preparation method thereof, and the gold stamping slurry is by including following parts by weight Raw material be made：Acrylic acid ester emulsion 60~80, deionized water 2~6, solvent 3~10, stabilizer 1~5, EVA hot-melt adhesive powder 10 ~20, silica 0.5~3, polyurethane defoamer 0.2~0.5, pH adjusting agent 0.1~0.5, preservative 0.1~0.2 and breast Change wetting agent 0.3~1, thickener 0.4~2.Its feature is to have used EVA thermal fusing powders to increase fastness, but EVA materials is water-fast Property is general, so being of limited application.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of gold stamping slurry and preparation method thereof, institute Stating gold stamping slurry can be as the sticker between orange cold foil and any cloth, and making stamp process is easy to operate, stamp is not tacky, thermoprint Temperature is low, has superelevation wash durability with its manufactured printing textile, and repeatedly washing is not faded, and does not lose mirror effect and hand Sense is soft, has good application prospect in weaving, paper product field.
To use following technical scheme up to this purpose, the present invention：
An object of the present invention is to provide a kind of gold stamping slurry, and the gold stamping slurry is in parts by weight by 55.8~92.2 parts Acrylic emulsion, 5~40 parts of thermal fusing powders, 0.3~0.8 part of curing agent, 1.5~3 parts of thickeners and 0.1~0.4 part of defoamer system Standby to obtain, the acrylic emulsion, thermal fusing powder, curing agent, the parts by weight sum of thickener and defoamer are 100 parts；Wherein, The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is methacrylic acid ethyl acetoacetate (AAEM) or DAAM, works as cross-linking monomer For methacrylic acid ethyl acetoacetate when, the parts by weight of adipic dihydrazide are 0.Use AAEM or ketone hydrazine crosslinked System, the self-crosslinking speed of glued membrane can be effectively improved, while its carbonyl produces with the anodized aluminium of orange cold foil and is bonded and assigns stamp production The more preferable fastness of product and elasticity.
The gold stamping slurry is in parts by weight by 55.8~92.2 parts of acrylic emulsions, 5~40 parts of thermal fusing powders, 0.3~0.8 part Curing agent, 1.5~3 parts of thickeners and 0.1~0.4 part of defoamer are prepared, as acrylic emulsion be 56 parts, 57 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 91 parts etc.；Thermal fusing powder be 6 parts, 8 parts, 10 parts, 12 parts, 15 Part, 20 parts, 25 parts, 30 parts or 35 parts；Curing agent is 0.4 part, 0.5 part, 0.6 part or 0.7 part etc.；Thickener be 1.6 parts, 1.8 Part, 2.0 parts, 2.2 parts, 2.5 parts or 2.8 parts etc.；Defoamer is 0.2 part or 0.3 part etc..The acrylic emulsion, thermal fusing powder, consolidate The parts by weight sum of agent, thickener and defoamer is 100 parts, such as 60 parts of acrylic emulsion, 37.3 parts of thermal fusing powder, curing agent 0.2 part of 0.5 part, 2 parts of thickener and defoamer；65 parts of acrylic emulsion, 32.1 parts of thermal fusing powder, 0.4 part of curing agent, thickener 2.2 parts and 0.3 part of defoamer；70 parts of acrylic emulsion, 26.8 parts of thermal fusing powder, 0.6 part of curing agent, 2.5 parts of thickener and defoaming 0.1 part of agent；0.2 part of 75 parts of acrylic emulsion, 21.3 parts of thermal fusing powder, 0.7 part of curing agent, 2.8 parts of thickener and defoamer；Propylene 0.2 part of 80 parts of yogurt liquid, 16.8 parts of thermal fusing powder, 0.5 part of curing agent, 2.5 parts of thickener and defoamer；86 parts of acrylic emulsion, 0.3 part of 10.5 parts of thermal fusing powder, 0.5 part of curing agent, 2.7 parts of thickener and defoamer.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：0.8~1.8 part of emulsifying agent, such as 0.9 Part, 1.0 parts, 1.2 parts, 1.3 parts, 1.4 parts or 1.6 parts etc.；60~70 parts of soft monomer, such as 61 parts, 62 parts, 63 parts, 65 parts, 67 parts Or 69 parts etc.；20~35 parts of hard monomer, such as 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or 34 parts；0.5~3 part of cross-linking monomer, Such as 0.8 part, 1.0 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.3 parts, 2.5 parts or 2.8 parts；3~5 parts of function monomer, such as 3.2 parts, 3.5 parts, 3.8 parts, 4.0 parts, 4.2 parts, 4.5 parts or 4.8 parts etc.；0.15~0.4 part of initiator, such as 0.2 part, 0.23 part, 0.25 Part, 0.28 part, 0.30 part, 0.35 part or 0.38 part etc.；0.3~1.4 part of nertralizer, such as 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 parts, 1.2 parts or 1.3 parts etc.；0.3~0.5 part of pH buffer, such as 0.32,0.35,0.38,0.40, 0.42nd, 0.45 or 0.48 etc.；0~2.4 part of adipic dihydrazide, such as 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1.0 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts or 2.2 parts etc.；88~115 parts of deionized water, such as 90 parts, 95 parts, 98 parts, 100 parts, 105 parts, 108 Part, 110 parts or 112 parts etc..
As preferable technical scheme, the acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is methacrylic acid ethyl acetoacetate or DAAM, when cross-linking monomer is methyl During acrylic acid ethyl acetoacetate, the parts by weight of adipic dihydrazide are 0.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier.Reactive emulsifier can reduce moving for small molecule Move, strengthen its water resistance；And phosphoric acid esters wedding agents can improve the adhesive force between glued membrane and orange cold foil.
Preferably, the phosphoric acid ester emulsifying agent is aliphatic alcohol polyoxyvinethene phosphate, such as sieve sub- RS610 and/ Or RS710.
Preferably, the reactive emulsifier is that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX's At least one of surfactant, wherein R are alkyl, such as methyl, ethyl, propyl group, butyl or amyl group, and n is 10~30, such as 12nd, 13,15,18,20,22,25 or 28 etc., X are H or SO3NH4。
The soft monomer is a kind of and mixture of butyl acrylate in ethyl acrylate or Isooctyl acrylate monomer.Typical case But nonrestrictive mixture is：The mixture of ethyl acrylate and butyl acrylate, Isooctyl acrylate monomer and butyl acrylate Mixture.
Preferably, the hard monomer is any one in methyl methacrylate, styrene and acrylonitrile or at least two Mixture.Typical but non-limiting mixture is：Methyl methacrylate and styrene, styrene and acrylonitrile, methyl Methyl acrylate, styrene and acrylonitrile, methyl methacrylate and acrylonitrile.
Preferably, the function monomer is the acrylic monomers containing cyclic structure and/or carboxy-containing acid group's acrylic acid list Body.
Preferably, the acrylic monomers containing cyclic structure is GMA and/or miscellaneous with urea The methacrylate-based monomer of cyclic group, the methacrylate-based monomer with urea heterocyclic group such as SIPOMER WAM- II and/or SIPOMER WAM-III.Acrylic monomers containing cyclic structure can improve wet adhesion so that gold stamping pulp-water Can't be washed off color.
Preferably, carboxy-containing acid group's acrylic monomers is acrylic acid, methacrylic acid and β-propyloic acrylic ester In any one or at least two mixture.Typical but non-limiting mixture is：Acrylic acid and methacrylic acid, third Olefin(e) acid and β-propyloic acrylic ester, methacrylic acid and β-propyloic acrylic ester, acrylic acid, methacrylic acid and β-carboxylic second Base acrylate.
The initiator is ammonium persulfate and/or potassium peroxydisulfate.
Preferably, the nertralizer is one kind or at least two mixture in ammoniacal liquor, ethylenediamine and diethanol amine.Allusion quotation Type but nonrestrictive mixture is：Ammoniacal liquor and ethylenediamine, ammoniacal liquor and diethanol amine, ethylenediamine and diethanol amine, ammoniacal liquor, second two Amine and diethanol amine.
Preferably, the pH buffer is sodium acid carbonate.
The thermal fusing powder is the mixture of any one or at least two in Silon, polyester powder and polyurethane powder.
Preferably, the particle diameter of the thermal fusing powder is 0~80 μm.
The thermal fusing powder melts as a phase after heating at a certain temperature with glued membrane, had both added glued membrane fastness, and had caused glue again Film is smooth and then causes gold stamping stamp to have mirror effect；Simultaneously using different type thermal fusing powder collocation, can adjust its fastness and Pliability.
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane.
Preferably, the thickener is association type polyurethane.
Preferably, the defoamer is polysiloxanes.
The second object of the present invention is to provide a kind of preparation method of gold stamping slurry as described above, the preparation method For：By the emulsifying agent of formula ratio, soft monomer, hard monomer, cross-linking monomer, function monomer, initiator, nertralizer, pH buffer, oneself Dihydrazi and deionized water be continuously added dropwise technique through pre-emulsification and pre-emulsion be made, backward pre-emulsion in add formula ratio Thermal fusing powder, curing agent, thickener and defoamer, you can obtain gold stamping slurry.
As preferable technical scheme, the preparation method of the gold stamping slurry comprises the following steps：
(1) by 60~70 parts of acrylate soft monomer, 20~35 parts of hard monomer, 3~5 parts of function monomer, emulsifying agent 0.5~ 1 part and 40~50 parts of deionized water, stir after mixing and are prepared into pre-emulsion；
(2) 0.1~0.3 part of initiator is dissolved in 5~10 parts of deionized water, is configured to initiator solution；
(3) in a kettle, 40~50 parts of deionized waters, 0.05~0.1 part of initiator solution, 0.3~0.8 part of breast are added Agent and 0.3~0.5 part of pH buffer, stir；Then 5~8 parts of pre-emulsion is added under agitation, is warming up to 88 ~90 DEG C are reacted, after blue light occurs in emulsion；112~120 parts of pre-emulsions and 4~5 parts of initiators are added dropwise into reactor Solution, the continuous 3h that is added dropwise are added；0.5~3 part of cross-linking monomer is dissolved in again the solution and 28 obtained in 3~5 parts of deionized waters ~30 parts of pre-emulsions are added dropwise together, and the continuous 0.5h that is added dropwise is added；It is warming up to 92~93 DEG C and 1~1.5h of insulation reaction；Finally will Temperature is down to less than 40 DEG C, regulation pH value to 6.5~7.0, adds 0.3~1.4 part of nertralizer and 0~2.4 part of adipic acid Two hydrazides, acrylic emulsion is obtained after warp thread net filtration；
(4) 5~40 parts of thermal fusing powder, 0.3~0.8 part of curing agent, 1.5~3 parts of increasings are sequentially added into acrylic emulsion Thick dose and 0.1~0.4 part of defoamer, obtain gold stamping slurry.
Step (1) the pre-emulsified time is 20~30min, such as 22min, 23min, 25min, 26min, 27min or 29min etc..
Preferably, the mesh number of step (3) described gauze is 120~180 mesh, such as 130 mesh, 140 mesh, 150 mesh, 160 mesh or 170 mesh etc..
Step (4) described cross-linking monomer is methacrylic acid ethyl acetoacetate (AAEM) or DAAM, when When cross-linking monomer is methacrylic acid ethyl acetoacetate, the parts by weight of adipic dihydrazide are 0.
Preferably, step (4) thermal fusing powder is added in pre-emulsion under the conditions of high-speed stirred.
Preferably, the speed of the stirring is 2000~3000r/min, such as 2200r/min, 2500r/min, 2800r/ Min or 2900r/min etc..
Preferably, the viscosity of step (4) described acrylic emulsion is 12000~15000mPas, as 12500mPas, 13000mPas, 13500mPas, 14000mPas or 14500mPas etc..
Compared with prior art, beneficial effects of the present invention are：
(1) gold stamping slurry provided by the invention has selected Polymerizable Emulsifier and phosphoric acid ester emulsifying agent, its aggretion type breast Agent can reduce the migration of small molecule, strengthen its water resistance；And phosphoric acid ester emulsifying agent can be improved between glued membrane and orange cold foil Adhesive force；
(2) gold stamping slurry provided by the invention selects ring-type function monomer, and main function is to improve wet adhesion so that scalds Gold paste washing is not faded；
(3) gold stamping slurry provided by the invention selects methacrylic acid ethyl acetoacetate (AAEM) or ketone hydrazine crosslinked System, the self-crosslinking speed of glued membrane can be effectively improved, while its carbonyl produces with the anodized aluminium of orange cold foil and is bonded and assigns stamp production The more preferable fastness of product and elasticity；
(4) gold stamping slurry provided by the invention use thermal fusing powder, melt after being heated because of thermal fusing powder at a certain temperature with glued membrane for One phase, glued membrane fastness was both added, and caused that glued membrane is smooth and then causes gold stamping stamp to have mirror effect again；Use inhomogeneity simultaneously The collocation of type thermal fusing powder, it can adjust its fastness and pliability.
The gold stamping slurry can make easy to operate, print during stamp as the sticker between orange cold foil and any cloth Flower surface is not tacky, blocking point is low, and blocking point is 130~140 DEG C, and manufactured printing textile is resistant to 60 DEG C, 2.5 hours Washing, at least 3 times washings do not fade, and do not lose mirror effect and soft not easy-to-draw quick-fried, have very well in weaving, paper product field Application prospect.
Embodiment
Technical scheme is further illustrated below by embodiment.
Embodiment 1
A kind of gold stamping slurry, the gold stamping slurry array by weight are mainly prepared by the following raw material：
The thermal fusing powder is Silon；The particle diameter of the thermal fusing powder is 0~80 μm, not including 0；
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane；The thickener is the poly- ammonia of association type Ester；The defoamer is polysiloxanes.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is DAAM.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier, and the phosphoric acid ester emulsifying agent is fatty alcohol Polyoxyethylene ether phosphate, the reactive emulsifier are that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX Surfactant, wherein R is methyl, n 30, X H.
The function monomer is the acrylic monomers containing cyclic structure, and the acrylic monomers containing cyclic structure is GMA.
The soft monomer is the mixture of ethyl acrylate and butyl acrylate.
The hard monomer is methyl methacrylate.
Described initiator is ammonium persulfate.
The nertralizer is ammoniacal liquor.
The pH buffer is sodium acid carbonate.
The preparation method of the gold stamping slurry comprises the following steps：
(1) by 70 parts of acrylate soft monomer, 20 parts of hard monomer, 3 parts of function monomer, 0.5 part of emulsifying agent and deionized water Stirred after 40 parts of mixing and be prepared into pre-emulsion；
(2) 0.1 part of initiator is dissolved in 5 parts of deionized water, is configured to initiator solution；
(3) in a kettle, 40 parts of deionized waters, 0.05 part of initiator solution, 0.3 part of emulsifying agent and 0.5 part are added PH buffer, stir；Then 5 parts of the pre-emulsion added under agitation in step (1), 88 DEG C is warming up to and is carried out instead Should；After blue light occurs in emulsion, 112 parts of pre-emulsions and 4 parts of initiator solutions are added dropwise into reactor, the continuous 3h that is added dropwise is added； 3 parts of solution being dissolved in 3 parts of deionized waters of cross-linking monomer are added dropwise together with 28 parts of pre-emulsions again, the continuous 0.5h that is added dropwise adds It is complete；It is warming up to 92 DEG C and insulation reaction 1.5h；Less than 40 DEG C are finally cooled the temperature to, regulation pH value to 6.5, adds 2.4 parts Adipic dihydrazide and 0.3 part of nertralizer, the acrylic acid that viscosity is 12000mPas is obtained after the gauze filtering of 180 mesh Emulsion；
(4) 92.2 parts of acrylic emulsions are sequentially added into 5 parts of thermal fusing powder, curing agent under 2000r/min stirring 0.4 part of 0.8 part, 1.6 parts of thickener and defoamer, obtain gold stamping slurry.
Embodiment 2
A kind of gold stamping slurry, the gold stamping slurry array by weight are mainly prepared by the following raw material：
The thermal fusing powder is polyester powder and polyurethane powder；The particle diameter of the thermal fusing powder is 0~80 μm, not including 0；
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane；The thickener is the poly- ammonia of association type Ester；The defoamer is polysiloxanes.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is methacrylic acid ethyl acetoacetate.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier, and the phosphoric acid ester emulsifying agent is fatty alcohol Polyoxyethylene ether phosphate, the reactive emulsifier are that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX Surfactant, wherein R is amyl group, n 10, X SO3NH4。
The function monomer is carboxy-containing acid group's acrylic monomers, and carboxy-containing acid group's acrylic monomers is acrylic acid.
The soft monomer is the mixture of ethyl acrylate and butyl acrylate.
The hard monomer is acrylonitrile.
Described initiator is potassium peroxydisulfate.
The nertralizer is diethanol amine.
The pH buffer is sodium acid carbonate.
The preparation method of the gold stamping slurry comprises the following steps：
(1) by 60 parts of acrylate soft monomer, 35 parts of hard monomer, 5 parts of function monomer, 1 part of emulsifying agent and deionized water 50 Stirred after part mixing and be prepared into pre-emulsion；
(2) 0.15 mass parts initiator is dissolved in the deionized water of 10 mass parts, is configured to initiator solution；
(3) in a kettle, 50 parts of deionized waters, 0.1 part of initiator solution, 0.8 part of emulsifying agent and 0.3 part of pH are added Buffer, stir；Then 8 parts of the pre-emulsion added under agitation in step (1), is warming up to 90 DEG C and is reacted； After blue light occurs in emulsion, 112 parts of pre-emulsions and 5 parts of initiator solutions are added dropwise into reactor, the continuous 3h that is added dropwise is added；Again 0.5 part of solution being dissolved in 5 parts of deionized waters of cross-linking monomer is added dropwise together with 30 parts of pre-emulsions, and the continuous 0.5h that is added dropwise is added； It is warming up to 92~93 DEG C and insulation reaction 1h；Less than 40 DEG C are finally cooled the temperature to, regulation pH value to 7.0, is added in 1.4 parts And agent, the acrylic emulsion that viscosity is 15000mPas is obtained after the gauze filtering of 120 mesh；
(4) 55.8 parts of acrylic emulsions are sequentially added into 40 parts of thermal fusing powder, curing agent under 3000r/min stirring 0.4 part of 0.8 part, 3 parts of thickener and defoamer, obtain gold stamping slurry.
Embodiment 3
A kind of gold stamping slurry, the gold stamping slurry array by weight are mainly prepared by the following raw material：
The thermal fusing powder is the mixture of Silon, polyester powder and polyurethane powder；The particle diameter of the thermal fusing powder is 0~80 μm, not including 0；
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane；The thickener is the poly- ammonia of association type Ester；The defoamer is polysiloxanes.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is DAAM.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier, and the phosphoric acid ester emulsifying agent is fatty alcohol Polyoxyethylene ether phosphate, the reactive emulsifier are that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX Surfactant, wherein R is alkyl, n 15, X H.
The function monomer is the acrylic monomers containing cyclic structure and carboxy-containing acid group's acrylic monomers.It is described containing The acrylic monomers of cyclic structure is GMA and the methacrylate-based monomer with urea heterocyclic group； Carboxy-containing acid group's acrylic monomers is the mixture of acrylic acid, methacrylic acid and β-propyloic acrylic ester.
The soft monomer is the mixture of ethyl acrylate and butyl acrylate.
The hard monomer is the mixture of methyl methacrylate, styrene and acrylonitrile.
Described initiator is ammonium persulfate and potassium peroxydisulfate.
The nertralizer is the mixture of ammoniacal liquor, ethylenediamine and diethanol amine.
The pH buffer is sodium acid carbonate.
The preparation method of the gold stamping slurry comprises the following steps：
(1) by 65 parts of acrylate soft monomer, 30 parts of hard monomer, 4 parts of function monomer, 0.6 part of emulsifying agent and deionized water Stirred after 45 parts of mixing and be prepared into pre-emulsion；
(2) 0.3 part of initiator is dissolved in 6 parts of deionized waters, is configured to initiator solution；
(3) in a kettle, 45 parts of deionized waters, 0.08 part of initiator solution, 0.4 part of emulsifying agent and 0.4 part are added PH buffer, stir；Then 7 parts of the pre-emulsion added under agitation in step (1), 89 DEG C is warming up to and is carried out instead Should；After blue light occurs in emulsion, 120 parts of pre-emulsions and 4.5 parts of initiator solutions are added dropwise into reactor, the continuous 3h that is added dropwise adds It is complete；2 parts of solution being dissolved in 4 parts of deionized waters of cross-linking monomer are added dropwise together with 29 parts of pre-emulsions again, 0.5h is continuously added dropwise Add；It is warming up to 92.5 DEG C and insulation reaction 1.8h；Less than 40 DEG C are finally cooled the temperature to, regulation pH value to 6.8, adds 1.2 The adipic dihydrazide and 1.0 parts of nertralizer of part, viscosity is obtained after the gauze filtering of 150 mesh as the third of 14500mPas Olefin(e) acid emulsion；
(4) 78.1 parts of acrylic emulsions are sequentially added into 20 parts of thermal fusing powder, curing agent under 2500r/min stirring 0.1 part of 0.3 part, 1.5 parts of thickener and defoamer, obtain gold stamping slurry.
Embodiment 4
A kind of gold stamping slurry, the gold stamping slurry array by weight are mainly prepared by the following raw material：
The thermal fusing powder is Silon；The particle diameter of the thermal fusing powder is 0~80 μm, not including 0；
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane；The thickener is the poly- ammonia of association type Ester；The defoamer is polysiloxanes.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is DAAM.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier, and the phosphoric acid ester emulsifying agent is fatty alcohol Polyoxyethylene ether phosphate, the reactive emulsifier are that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX At least one of surfactant, wherein R is propyl group, n 20, X SO3NH4。
The function monomer is the acrylic monomers containing cyclic structure and carboxy-containing acid group's acrylic monomers.It is described containing The acrylic monomers of cyclic structure is GMA and the methacrylate-based monomer with urea heterocyclic group； Carboxy-containing acid group's acrylic monomers is acrylic acid.
The soft monomer is the mixture of Isooctyl acrylate monomer and butyl acrylate.
The hard monomer is the mixture of methyl methacrylate, styrene and acrylonitrile.
Described initiator is potassium peroxydisulfate.
The nertralizer is the mixture of ethylenediamine and diethanol amine.
The pH buffer is sodium acid carbonate.
The preparation method of the gold stamping slurry comprises the following steps：
(1) by 68 parts of acrylate soft monomer, 25 parts of hard monomer, 3 parts of function monomer, 0.5 part of emulsifying agent and deionized water Stirred after 40 parts of mixing and be prepared into pre-emulsion；
(2) 0.3 part of initiator is dissolved in 5 parts of deionized waters, is configured to initiator solution；
(3) in a kettle, 40 parts of deionized waters, 0.08 part of initiator solution, 0.5 part of emulsifying agent and 0.4 part are added PH buffer, stir；Then 8 parts of the pre-emulsion added under agitation in step (1), 90 DEG C is warming up to and is carried out instead Should；After blue light occurs in emulsion, 115 parts of pre-emulsions and 5 parts of initiator solutions are added dropwise into reactor, the continuous 3h that is added dropwise is added； 2 parts of solution being dissolved in 5 parts of deionized waters of cross-linking monomer are added dropwise together with 30 parts of pre-emulsions again, the continuous 0.5h that is added dropwise adds It is complete；It is warming up to 92 DEG C and insulation reaction 1.5h；Finally cool the temperature to less than 40 DEG C, regulation pH value to 7.0, add oneself of 2 parts Dihydrazi and 0.5 part of nertralizer, the propylene yogurt that viscosity is 14000mPas is obtained after the gauze filtering of 150 mesh Liquid；
(4) 66.7 parts of acrylic emulsions are sequentially added into 30 parts of thermal fusing powder, curing agent under 2600r/min stirring 0.2 part of 0.6 part, 2.5 parts of thickener and defoamer, obtain gold stamping slurry.
Embodiment 5
A kind of gold stamping slurry, the gold stamping slurry array by weight are mainly prepared by the following raw material：
The thermal fusing powder is polyurethane powder；The particle diameter of the thermal fusing powder is 0~80 μm, not including 0；
The curing agent is 3- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane；The thickener is the poly- ammonia of association type Ester；The defoamer is polysiloxanes.
The acrylic emulsion is mainly prepared by the following raw material in parts by weight：
The cross-linking monomer is methacrylic acid ethyl acetoacetate.
The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier, and the phosphoric acid ester emulsifying agent is fatty alcohol Polyoxyethylene ether phosphate, the reactive emulsifier are that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nOX At least one of surfactant, wherein R is alkyl, n 25, X SO3NH4。
The function monomer is the acrylic monomers containing cyclic structure.The acrylic monomers containing cyclic structure is Methacrylate-based monomer with urea heterocyclic group；Carboxy-containing acid group's acrylic monomers is β-propyloic acrylic ester.
The soft monomer is the mixture of ethyl acrylate and butyl acrylate.
The hard monomer is methyl methacrylate.
Described initiator is potassium peroxydisulfate.
The nertralizer is ammoniacal liquor.
The pH buffer is sodium acid carbonate.
The preparation method of the gold stamping slurry comprises the following steps：
(1) by 62 parts of acrylate soft monomer, 30 parts of hard monomer, 4 parts of function monomer, 0.8 part of emulsifying agent and deionized water Stirred after 47 parts of mixing and be prepared into pre-emulsion；
(2) 0.2 part of initiator is dissolved in 10 parts of deionized waters, is configured to initiator solution；
(3) in a kettle, 50 parts of deionized waters, 0.08 part of initiator solution, 0.7 part of emulsifying agent and 0.3 part are added PH buffer, stir；Then 8 parts of the pre-emulsion added under agitation in step (1), 88 DEG C is warming up to and is carried out instead Should；After blue light occurs in emulsion, 118 parts of pre-emulsions and 5 parts of initiator solutions are added dropwise into reactor, the continuous 3h that is added dropwise is added； 1 part of solution being dissolved in 3 parts of deionized waters of cross-linking monomer is added dropwise together with 30 parts of pre-emulsions again, the continuous 0.5h that is added dropwise adds It is complete；It is warming up to 93 DEG C and insulation reaction 1h；Less than 40 DEG C are finally cooled the temperature to, regulation pH value to 6.5, is added in 1.0 parts And agent, the acrylic emulsion that viscosity is 13000mPas is obtained after the gauze filtering of 180 mesh；
(4) 77.2 parts of acrylic emulsions are sequentially added into 20 parts of thermal fusing powder, curing agent under 3000r/min stirring 0.3 part of 0.5 part, 2 parts of thickener and defoamer, obtain gold stamping slurry.
Comparative example 1
In addition to DAAM and adipic dihydrazide is not contained in the raw material of acrylic emulsion, the comparative example 1 It is same as Example 4.
Comparative example 2
In addition to methacrylic acid ethyl acetoacetate (AAEM) is not contained in the raw material of acrylic emulsion, the comparative example 2 It is same as Example 5.
Comparative example 3
In addition to the emulsifying agent in acrylic emulsion is phosphoric acid esters wedding agents, the comparative example 3 is same as Example 4.
Comparative example 4
In addition to the emulsifying agent in acrylic emulsion is reactive emulsifier, the comparative example 4 is same as Example 4.
Comparative example 5
Except the emulsifying agent in acrylic emulsion is reactive emulsifier, and double third is not contained in the raw material of acrylic emulsion Outside ketone acrylamide, methacrylic acid ethyl acetoacetate and adipic dihydrazide, the comparative example 5 is same as Example 4.
Gold stamping slurry made from embodiment 1~5 and comparative example 1~5 is subjected to performance test, test result is as shown in table 1.
Table 1
Note：Wash water fastness is tested：Soap water is washed 2.5 hours；
Mirror effect is evaluated：0 grade：Mirror effect, there is reflecting effect；1-2 levels：Surfacing, but mirror effect does not protrude； 3-4 levels：There are small noise, no-reflection effect in surface；5 grades：Rough surface out-of-flatness.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.

Claims (21)

  1. A kind of 1. gold stamping slurry, it is characterised in that the gold stamping slurry in parts by weight by 55.8~92.2 parts of acrylic emulsions, 5~ 40 parts of thermal fusing powders, 0.3~0.8 part of curing agent, 1.5~3 parts of thickeners and 0.1~0.4 part of defoamer are prepared, the propylene Yogurt liquid, thermal fusing powder, curing agent, the parts by weight sum of thickener and defoamer are 100 parts；Wherein, the acrylic emulsion Mainly it is prepared in parts by weight by the following raw material：
    The cross-linking monomer is methacrylic acid ethyl acetoacetate or DAAM, when cross-linking monomer is metering system During sour ethyl acetoacetate, the parts by weight of adipic dihydrazide are 0；
    The emulsifying agent is phosphoric acid esters wedding agents and reactive emulsifier；
    The phosphoric acid esters wedding agents are aliphatic alcohol polyoxyvinethene phosphate；
    The reactive emulsifier is that molecular formula is CH2=CHCH2OCH2CH(ROCH2)(OCH2CH2)nIn OX surfactant At least one, wherein R is alkyl, and n is that 10~30, X is H or SO3NH4。
  2. 2. gold stamping slurry according to claim 1, it is characterised in that the acrylic emulsion is in parts by weight mainly by as follows Raw material is prepared：
    The cross-linking monomer is methacrylic acid ethyl acetoacetate or DAAM, when cross-linking monomer is metering system During sour ethyl acetoacetate, the parts by weight of adipic dihydrazide are 0.
  3. 3. gold stamping slurry according to claim 1, it is characterised in that the soft monomer is that ethyl acrylate or acrylic acid are different pungent A kind of mixture of and butyl acrylate in ester.
  4. 4. gold stamping slurry according to claim 1, it is characterised in that the hard monomer is methyl methacrylate, styrene With any one in acrylonitrile or at least two mixture.
  5. 5. gold stamping slurry according to claim 1, it is characterised in that the function monomer is the acrylic acid containing cyclic structure Monomer and/or carboxy-containing acid group's acrylic monomers.
  6. 6. gold stamping slurry according to claim 5, it is characterised in that the acrylic monomers containing cyclic structure is methyl Glycidyl acrylate and/or the methacrylate-based monomer with urea heterocyclic group；
  7. 7. gold stamping slurry according to claim 5, it is characterised in that carboxy-containing acid group's acrylic monomers be acrylic acid, In methacrylic acid and β-propyloic acrylic ester any one or at least two mixture.
  8. 8. gold stamping slurry according to claim 1, it is characterised in that the initiator is ammonium persulfate and/or potassium peroxydisulfate.
  9. 9. gold stamping slurry according to claim 1, it is characterised in that the nertralizer is in ammoniacal liquor, ethylenediamine, diethanol amine One kind or at least two mixture.
  10. 10. gold stamping slurry according to claim 1, it is characterised in that the pH buffer is sodium acid carbonate.
  11. 11. gold stamping slurry according to claim 1, it is characterised in that the thermal fusing powder is Silon, polyester powder and poly- ammonia In ester powder any one or at least two mixture.
  12. 12. gold stamping slurry according to claim 1, it is characterised in that the particle diameter of the thermal fusing powder is 0~80 μm, is not 0.
  13. 13. gold stamping slurry according to claim 1, it is characterised in that the curing agent is 3- (2,3- the third oxygen of epoxy) propyl group Trimethoxy silane.
  14. 14. gold stamping slurry according to claim 1, it is characterised in that the thickener is association type polyurethane.
  15. 15. gold stamping slurry according to claim 1, it is characterised in that the defoamer is polysiloxanes.
  16. 16. the preparation method of gold stamping slurry according to claim 1, it is characterised in that the preparation method is：By formula ratio Emulsifying agent, soft monomer, hard monomer, cross-linking monomer, function monomer, initiator, nertralizer, pH buffer, adipic dihydrazide Technique is continuously added dropwise through pre-emulsification with deionized water acrylic emulsion is made, then the hot melt of formula ratio is added into acrylic emulsion Powder, curing agent, thickener and defoamer, you can obtain gold stamping slurry.
  17. 17. preparation method according to claim 16, it is characterised in that the preparation method comprises the following steps：
    (1) by 60~70 parts of acrylate soft monomer, 20~35 parts of hard monomer, 3~5 parts of function monomer, 0.5~1 part of emulsifying agent With 40~50 parts of deionized water, stirred after mixing and be prepared into pre-emulsion；
    (2) 0.1~0.3 part of initiator is dissolved in 5~10 parts of deionized water, is configured to initiator solution；
    (3) in a kettle, 40~50 parts of deionized waters, 0.05~0.1 part of initiator solution, 0.3~0.8 part of emulsifying agent are added And 0.3~0.5 part of pH buffer, stir；Then 5~8 parts of pre-emulsion is added under agitation, is warming up to 88~90 DEG C reacted, after blue light occurs in emulsion；112~120 parts of pre-emulsions and 4~5 parts of initiator solutions are added dropwise into reactor, The continuous 3h that is added dropwise is added；Again cross-linking monomer 0.5~3 part be dissolved in the solution obtained in 3~5 parts of deionized waters and 28~30 parts Pre-emulsion is added dropwise together, and the continuous 0.5h that is added dropwise is added；It is warming up to 92~93 DEG C and 1~1.5h of insulation reaction；Finally temperature is dropped To less than 40 DEG C, regulation pH value to 6.5~7.0, the nertralizer and 0~2.4 part of adipic dihydrazide of 0.3~1.4 part of addition, Acrylic emulsion is obtained after warp thread net filtration；
    (4) 5~40 parts of thermal fusing powder, 0.3~0.8 part of curing agent, 1.5~3 parts of thickeners is sequentially added into acrylic emulsion With 0.1~0.4 part of defoamer, gold stamping slurry is obtained.
  18. 18. preparation method according to claim 17, it is characterised in that step (1) the pre-emulsified time be 20~ 30min。
  19. 19. preparation method according to claim 17, it is characterised in that the mesh number of step (3) described gauze be 120~ 180 mesh.
  20. 20. preparation method according to claim 17, it is characterised in that step (4) described thermal fusing powder is in high-speed stirred bar Added under part in acrylic emulsion；The speed of the stirring is 2000~3000r/min.
  21. 21. preparation method according to claim 17, it is characterised in that the viscosity of step (4) described acrylic emulsion is 12000~15000mPas.
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CN107880208B (en) * 2017-12-12 2020-06-26 杭州龙驹合成材料有限公司 Gold stamping slurry emulsion and preparation method thereof
CN108360273A (en) * 2018-02-05 2018-08-03 山东黄河三角洲纺织科技研究院有限公司 A kind of processing method of metallic Chinese flax fabric
CN108411651B (en) * 2018-03-20 2020-09-11 惠州长联新材料科技有限公司 Slurry for gold stamping and preparation method and application thereof
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