CN107033671A - It is a kind of for the aqueous dual-component adhesive of paint ink and application - Google Patents
It is a kind of for the aqueous dual-component adhesive of paint ink and application Download PDFInfo
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- CN107033671A CN107033671A CN201710290899.9A CN201710290899A CN107033671A CN 107033671 A CN107033671 A CN 107033671A CN 201710290899 A CN201710290899 A CN 201710290899A CN 107033671 A CN107033671 A CN 107033671A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Abstract
It is specially a kind of for the aqueous dual-component adhesive of paint ink and application the present invention relates to for digit printing paint ink.Aqueous dual-component adhesive is that component A and component B is constituted, by 3:4‑20:1 mass ratio mixing；Wherein, component A is the one or more in the aqueous polyurethane with amino or hydroxyl, the water polyacrylic acid with amino or hydroxyl, the aqueous acrylic modified polyurethane with amino or hydroxyl, and component B is aqueous blocked polyisocyanate.Aqueous dual-component adhesive of the present invention is as the adhesive resin in paint ink, binding material between pigment and fabric during for textile digital ink-jet.Component A has hydroxyl or amino active group, in digital ink-jet Post isothermal treatment, and polymerisation is carried out with the isocyanate group that is unsealed in component B, and the glued membrane of formation can assign dry, fastness to wet rubbing, the washing fastness and feel of PRINTED FABRIC well.
Description
Technical field
The present invention relates to for digit printing paint ink, specially a kind of aqueous dual-component for paint ink is bonded
Agent and application.
Background technology
Digital printing technology has easy to operate, low, high repayment the clear superiority of pollution, is that the development of following printing and dyeing becomes
Gesture.Pigment printing ink has, sewage discharge few the advantages of simple suitable for different fibers, pre-treatment and postfinishing process,
It is the main development direction of digit printing.After the subject matter of the digital pigment printing application of restriction now is paint ink stamp
Crock fastness is low, especially the low shortcoming of fastness to wet rubbing.Adhesive in paint ink for paint ink accounting it is maximum into
Point, it is to influence the principal element of the performances such as ink fastness, feel.Adhesive for fabric pigment printing is mostly polymer breast
Liquid, is adapted to the adhesive of the conventional pigment stamp nothing in terms of feel, suppleness, transparency, adhesiveness, particle diameter, particle diameter distribution
Method meets the requirement of digital pigment printing.
Paint ink adhesive also has relevant report in recent years：Patent US70301175 is reported with polyacrylate breast
The paint ink of bonding agent, for the coloring of the plastic cement materials such as PE, PVC, PU, dry fastness and water when being applied on fabric
Wash fastness not ideal enough.Patent US2005182154A reports paint ink using aqueous polyurethane as adhesive in fabric
Application on digit printing, and investigated the washing fastness of PRINTED FABRIC.Patent CN200510040114.X,
It is that dispersant and sticking agent prepare pigment ink-jet inkses that CN200510040115.4, which is reported using carboxylic acid-based copolymer, by poly-
Esterification and crosslinking occurs for carboxylic acid and polyol hydroxyls in carboxylic acid, pigment particles is anchored on base material, has color jail in need
Degree.United States Patent (USP) US6902780 is disclosed first to use and pre-processed to after fabric coating processing, improving the side of ink-jet printed color fastness
Method.Crosslinking agent is added in pigment ink-jetting printing ink by patent CN200710024154.4, firm to improve dry, wet friction
Degree, but effect is still undesirable, fastness to wet rubbing only has 2-2.5 grades, 3-4 grades of dry fastness.In order to meet current people couple
The demand of high-quality PRINTED FABRIC, the present invention develops that PRINTED FABRIC is dry, wet and the more excellent ink of washing fastness performance glues
Mixture, and be applied to method and inquired into.
The content of the invention
It is an object of the invention to provide a kind of for the aqueous dual-component adhesive of paint ink and application.
To achieve the above object, the present invention use technical scheme for：
A kind of aqueous dual-component adhesive for paint ink, aqueous dual-component adhesive is component A and component B groups
Into by 3:4-20:1 mass ratio mixing；Wherein, component A is the aqueous polyurethane with amino or hydroxyl, with amino or hydroxyl
One or more in the water polyacrylic acid of base, the aqueous acrylic modified polyurethane with amino or hydroxyl, component B is
Aqueous blocked polyisocyanate.
The aqueous polyurethane with amino or hydroxyl is soft segment polyester, diisocyanate, hydrophilic monomer, chain extender and
Crosslinking agent presses 50-80:10-30：2-6:0-3:React and obtain under 0-3 mass ratios.
It is further：Soft segment polyester carries out polymerisation with diisocyanate at 70-90 DEG C, treats that CNO contents reach reason
During by value, solvent (solvent is acetone, ethyl acetate or butanone), hydrophilic monomer, chain extension are sequentially added in obtained performed polymer
Agent continues reaction to terminal at 40-70 DEG C, obtains the aqueous polyurethane dispersion with amino or hydroxyl.
The soft segment polyester is one or more of mixing in polyester diol；Hydrophilic monomer is sulfonic group monomer, carboxylic
Acid-based monomers or PEO；Crosslinking agent is trihydroxylic alcohol, tertiary amine or tetraamine compound；Chain extender is C2-C8Straight chain or branch
The dihydric alcohol or diamine of chain.
Further soft segment polyester diol is PCDL, polyester adipate dihydric alcohol, polycaprolactone two
One or both of first alcohol；Wherein much further preferably from poly- carbonic acid hexylene glycol ester dihydric alcohol, poly- carbonic acid DOPCP two
First alcohol, poly- carbonic acid hexylene glycol DOPCP dihydric alcohol, polyadipate hexylene glycol ester dihydric alcohol, polyneopentyl glycol adipate two
One in first alcohol, polyadipate hexylene glycol DOPCP dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polycaprolactone diols
Plant or two kinds.
Hydrophilic monomer is sulfonic group monomer, carboxylic acid group's monomer or PEO；Further for dihydromethyl propionic acid or
AAS。
Described chain extender is C2-C8 straight or brancheds dihydric alcohol, binary amine compound, be further ethylene glycol,
Butanediol, hexylene glycol, diethylamine or IPD.
Crosslinking agent be trihydroxylic alcohol, tertiary amine or tetraamine compound, be further Glycerin, diethylenetriamine or
Triethylene tetramine.
The water polyacrylic acid with amino or hydroxyl is polymerized monomer in the presence of emulsifying agent, poly- through emulsion
Close gained；Wherein, polymerized monomer is butyl acrylate, octadecyl acrylate, hydroxy-ethyl acrylate, methyl acrylate, acrylic acid
In two or more.
It is further that emulsifying agent is well mixed (1%-5% that wherein weight of emulsifying agent is water) with water, obtains emulsifying agent
Solution.Polymerized monomer is first to be evaporated off respectively after polymerization inhibitor, is uniformly mixed, monomer mixture is made.Above-mentioned 1/3 is taken respectively
The monomer mixture of the emulsifier solution of (quality), 1/3 (quality), adds initiator when being warming up to 70-100 DEG C and triggers, then
Keep at this temperature, while emulsifier solution, monomer mixture and the water of above-mentioned remaining 2/3 (quality) is added dropwise, control drop
Acceleration.The follow-up continuous insulation reaction of completion of dropping is to polymerizeing completion.
Polymerized monomer is in butyl acrylate, octadecyl acrylate, hydroxy-ethyl acrylate, methyl acrylate, acrylic acid
Two kinds and two or more (certain polymerization inhibitor can be added during general acrylic ester monomer market sale, prevents from storing and transports
Shi Juhe, should be evaporated off in advance before.).
The emulsifying agent is OP-10 and/or lauryl sodium sulfate (ratio is any during mixing).
The aqueous acrylic modified polyurethane with amino or hydroxyl is with hydrophilic radical base polyurethane prepolymer for use as warp
After hydroxy ethyl methacrylate end-blocking, radical polymerization is carried out then by emulsification with acrylate monomer, is obtained.
Furtherly specific reaction condition is that polyester diol is with diisocyanate acid esters, hydrophilic monomer at 70-90 DEG C
Polymerisation is carried out, when CNO contents reach theoretical value, the performed polymer of obtained NCO end-blockings reacts with hydroxy-ethyl acrylate, obtains
The performed polymer blocked to double bond, adds water emulsification, then in the presence of catalyst (catalyst be the different cyanogen in heptan of azo two) with acrylic acid
Ester monomer obtains acrylic acid modified polyurethane aqueous dispersion body in carrying out polymerisation at 70-100 DEG C.
Polyester diol can be one in PCDL, polyester adipate dihydric alcohol, polycaprolactone diols
Plant or two kinds.Wherein preferred poly- carbonic acid hexylene glycol ester dihydric alcohol, poly- carbonic acid DOPCP dihydric alcohol, poly- carbonic acid hexylene glycol new penta
Diol ester dihydric alcohol, polyadipate hexylene glycol ester dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, polyadipate hexylene glycol are new
It is one or two kinds of in pentadiol ester dihydric alcohol, poly adipate succinic acid ester dihydric alcohol, polycaprolactone diols.
Hydrophilic monomer is sulfonic group monomer, carboxylic acid group's monomer or PEO；Wherein preferred dihydromethyl propionic acid or
AAS。
Acrylate monomer is butyl acrylate, octadecyl acrylate, hydroxy-ethyl acrylate, methyl acrylate, acrylic acid
In two kinds and it is two or more.
The polyisocyanate ester aqueous dispersion of end-blocking of the present invention is that blocked polyisocyanate dissipates acquisition through moisture；Wherein,
Blocked polyisocyanate is by 2.8-3 by diisocyanate polymer, hydrophilic monomer, end-capping reagent:0.9-1.1:1.8-2.2 (rubs
You compare) reaction acquisition.
Wherein two isocyanic acid acid esters polymers, are the dimerization of diisocyanate, trimerization, four poly- and five polyacetylene compounds, optimal
For the three, tetramer, wherein the three, tetramer can be diisocyanate from polyacetylene compound or addition product, addition product is two isocyanides
Acid esters and trimethylolpropane or pentaerythrite addition product.Described diisocyanate is in IPDI, HDI, HMDI, TDI, MDI
One kind, optimal is IPDI and HDI.
Hydrophilic monomer is sulfonic group monomer, carboxylic acid group's monomer or PEO；Wherein preferred dihydromethyl propionic acid or
AAS。
End-capping reagent is the end-capping reagent containing isocyano, and the end-capping reagent containing isocyano is imidazoles or oxime blocking agent.It is excellent
Select methyl ethyl ketoxime, acetoxime, dibutyl ketoxime；3,5 methylimidazoles, imidazoles, 2-ethyl-4-methylimidazole.
Specific reaction condition is, diisocyanate autohemagglutination polymer and end-capping reagent in the presence of 10-50 DEG C, solvent respectively with
After end-capping reagent and hydrophilic monomer reaction, obtained compound carries out moisture and dissipated, and obtains polyisocyanate ester aqueous dispersion.Or two isocyanides
After acid esters is polymerize with trimethylolpropane or pentaerythrite, then respectively with after end-capping reagent and hydrophilic monomer reaction, obtaining
Compound carries out moisture and dissipated, and obtains polyisocyanate ester aqueous dispersion.
Described component A, B average grain diameter is 20-200nm, preferably 40-150nm, numerial code spray drawing can be met completely smooth
Property requirement (effective grain size that component A, B can be controlled by hydrophilic monomer addition).
Above-mentioned adhesive is used for the preparation of paint ink, because the moisture that binder component A and B are anionic property dissipates
Body, after being simply mixed, stirs, then is added by the final drop mass 8-20% of accounting amount into mulser, protects
Humectant, bactericide, cosolvent, pH value regulator, defoamer, surfactant and water routinely ink set ratio add after,
Turn in 8000-10000/min revolutions under emulsify mixing in 20-30 minute at a high speed, be then under this speed addition dispersible pigment color paste after
Continuous emulsification 30-60 minutes, obtains paint ink.
A kind of application of aqueous dual-component adhesive for paint ink, described adhesive answering in paint ink
With.
Specially：Binder component A and B are well mixed according to the above ratio, then by accounting for ink gross mass 8-20%'s
Amount add into mulser, then successively by NMF, bactericide, cosolvent, pH value regulator, defoamer, surfactant and
Routinely ink set ratio is added water, and mixing in 20-30 minutes is emulsified at a high speed under 8000-10000 turns/min revolutions after addition,
Then it is that dispersible pigment color paste is added under this speed to be continued to emulsify 30-60 minutes, obtains paint ink.
The paint ink acts on cotton using digital ink-jet mode, on polyester-cotton fabric after, be heat-treated at 120-150 DEG C solid
Color.
Advantage for present invention：
Aqueous double-component adhesive of the present invention, which may be added to that, is used as its adhesive resin in paint ink, for textile number
Binding material between pigment and fabric during code ink-jet, component A and component B act synergistically, had in stamp high temperature laking process
PRINTED FABRIC color fastness, including dry, fastness to wet rubbing, washing fastness are improved to effect, simultaneously because polyurethane structural feature,
Impart the good feel of fabric.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values also belong to the application appended claims and limited
Scope.
Aqueous dual-component adhesive of the present invention is as the adhesive resin in paint ink, during for textile digital ink-jet
Binding material between pigment and fabric.Component A has hydroxyl or amino active group, in digital ink-jet Post isothermal treatment, with group
The isocyanate group unsealed in part B carries out polymerisation, and the glued membrane of formation can assign dry, the wet friction jail of PRINTED FABRIC well
Degree, washing fastness and feel.
Embodiment 1 (component A preparation)
11.4 grams of the polyadipate hexylene glycol ester dihydric alcohol (molecular weight 1140) melted in advance is added in four-hole boiling flask,
After 120 DEG C of vacuum dehydration 1 hour, be cooled to 50 DEG C, add 4.7 grams of polyisocyanates IPDI, it is well mixed after be warming up to 80 DEG C
Left and right stops when reacting to theory residue NCO, cooling, adds 20.0 grams of acetone, 0.86 gram of dihydromethyl propionic acid DMPA, heating
To 50 DEG C, when reacting to theory residue CNO, 40 DEG C are down to, 0.1 gram of ethylenediamine, 0.1 gram of IPD and three is sequentially added
0.2 gram of ethene tetramine, be maintained at 40 DEG C reaction 30 minutes after, add 0.8 gram of triethylamine, add water at a high speed emulsification 30 minutes, decompression
Distillation sloughs solvent and produces aqueous polyurethane dispersion, particle diameter 78.9nm, pH value 7.8.
Theoretical NCO content computational methods (following examples are same)：
NCO theory=[molNCO-molOH] * 42/M
M is the gross mass of reaction system
MolNCO is the total mole number of isocyano
MolOH is the total mole number of hydroxyl
Middle control NCO content analysis test method：
Weigh sample (2 ± 0.2) g (accurately to 0.001g, NCO content be more than 20% when, weigh 1 gram or so of sample) in
In 100ml titration cup, 25ml ethyl acetate is added, shaking up makes dissolving, and 10ml dibutyl amine-first is accurately added with bottleneck charger
Benzole soln.After fully shaking up, after placing 30 minutes, it is placed on potentiometric titrimeter, is titrated with the method set, standard
Solution is 0.5mol/L ethanol solution hydrochlorides, and instrument automatic result of calculation and can be shown on screen and (do sky in the same manner
White experiment).[using a few drop bromocresol greens as indicator, titrated with 0.5mol/lHCL standard liquids, when solution is by blueness change yellow
For terminal.And do blank test.]
As a result calculation formula：
÷ m × 100 of NCO%=(V0-V1) × c × 0.042
In formula:V0 --- blank consumes the volume of HCL standard liquids, (ml)；
V1 --- sample consumes the volume of HCL standard liquids, (ml)；
C --- the concentration of HCL standard liquids, (mol/L)；
The quality of m --- sample, (g).
Embodiment 2 (component A preparation)
By 10.0 grams of the poly adipate succinic acid ester dihydric alcohol (molecular weight 1000) melted in advance, add in four-hole boiling flask,
After 120 DEG C of vacuum dehydration 1 hour, 50 DEG C are cooled to, 4.5 grams of polyisocyanates IPDI, 0.32 gram of trimethylolpropane is added,
Stop when 80 DEG C or so reactions are warming up to after well mixed to theory residue NCO, be cooled to 40 DEG C, add 20.0 grams of acetone, two
0.80 gram of hydroxymethyl propionic acid DMPA, is warming up to 50 DEG C, when reacting to theory residue CNO, adds 0.4 gram of hexylene glycol, until infrared
Display is without CNO peaks.Add water emulsification 30 minutes at a high speed, obtained dispersion, and vacuum distillation sloughs solvent and obtains poly- containing hydroxyl
Urethane aqueous dispersion, particle diameter 85.6nm, pH value 7.6.
Embodiment 3 (component A preparation)
9.8 grams of the poly- carbonic acid hexylene glycol ester dihydric alcohol (molecular weight 980) melted in advance is added in four-hole boiling flask, 120 DEG C
After vacuum dehydration 1 hour, 50 DEG C are cooled to, IPDI3.2 grams of polyisocyanates, 1.0 grams of HDI is added, is warming up to after being well mixed
Stop when 90 DEG C or so reactions are to theory residue NCO, cool, add 20.0 grams of butanone, 0.86 gram of dihydromethyl propionic acid DMPA,
50 DEG C are warming up to, when reacting to theory residue CNO, 0.5 gram of hexylene glycol, 0.2 gram of trimethylolpropane, reaction to infrared light is added
Untill spectrum display is without CNO peaks, add water emulsification 30 minutes at a high speed, obtained dispersion, and vacuum distillation is sloughed solvent and obtained containing hydroxyl
The polyurethane aqueous dispersion body of base, particle diameter 54.9nm, pH value 7.5.
Embodiment 4 (component A preparation)
20.0 grams of the acid esters dihydric alcohol (molecular weight 2000) in oneself that gathers melted in advance is added in four-hole boiling flask, 120 DEG C true
After sky dehydration 1 hour, 50 DEG C are cooled to, 3.8 grams of polyisocyanates HDI is added, 80 DEG C or so reactions are warming up to after being well mixed
Stop during to theory residue NCO, cool, add 28.0 grams of acetone, stir.Start that 0.42 gram of ethylenediamine, different Fo Er is added dropwise
1.2 grams of 0.1 gram of ketone diamines and AAS, after being maintained at 40 DEG C of reactions 30 minutes, add water emulsification 30 minutes, vacuum distillation at a high speed are sloughed
Solvent is obtained containing amino aqueous polyurethane aqueous dispersion, particle diameter 90.6nm, pH value 7.0.
Embodiment 5 (component A preparation)
By the poly- carbonic acid melted in advance sour hexylene glycol DOPCP dihydric alcohol (molecular weight 1000, hexylene glycol：Neopentyl glycol
=5:5) 10.0 grams add in four-hole boiling flasks, after 115 DEG C of vacuum dehydration 1 hour, are cooled to 50 DEG C, add polyisocyanates IPDI
4.5 grams, stop when 80 DEG C or so reactions are warming up to after being well mixed to theory residue NCO, cool, add 20.0 grams of acetone, two
0.8 gram of hydroxymethyl propionic acid DMPA, is warming up to 50 DEG C, when reacting to theory residue CNO, is down to 40 DEG C, sequentially adds ethylenediamine
0.2 gram and 0.2 gram of triethylene tetramine, after being maintained at 40 DEG C of reactions 30 minutes, add 0.8 gram of triethylamine, add water emulsification 30 at a high speed
Minute, obtained dispersion, vacuum distillation are sloughed solvent and obtained containing amino aqueous polyurethane aqueous dispersion, particle diameter 58.6nm,
PH value 7.8.
Embodiment 6 (component A preparation)
By 5.0 grams of the polyadipate hexylene glycol ester dihydric alcohol (molecular weight 1000) melted in advance and polycaprolactone diols
5.7 grams of (molecular weight 1140) is added in four-hole boiling flasks, after 115 DEG C of vacuum dehydration 1 hour, is cooled to 50 DEG C, is added polyisocyanic acid
4.45 grams of ester IPDI, stops when 80 DEG C or so reactions are warming up to after being well mixed to theory residue NCO, cools, add acetic acid second
20.0 grams of ester, 0.72 gram of dihydromethyl propionic acid DMPA, are warming up to 50 DEG C, when reacting to theory residue CNO, are down to 40 DEG C, addition
0.2 gram of 0.2 gram of ethylenediamine, 0.1 gram of IPD and diethylenetriamine, be maintained at 40 DEG C reaction 30 minutes after, add hydroxyl
0.8 gram of base ethamine, add water emulsification 30 minutes at a high speed, obtained dispersion, and vacuum distillation sloughs solvent and obtains poly- containing amino
Urethane aqueous dispersion, particle diameter 66.8nm, pH value 7.7.
Embodiment 7 (component A preparation)
By IPDI4.5 grams, 10.0 grams of PCDL (molecular weight 1000) is added equipped with thermometer, with stirring
In three-necked flask, 80 DEG C are warming up to, insulation reaction to theoretical NCO content adds DMPA1.0 grams, and continuation, which is reacted to theoretical NCO, to be contained
Amount, adds 1.51 grams of hydroxy-ethyl acrylate, when in system infrared display be substantially not present-NCO group when, be cooled to 30 degree it is left
The right side, or so speed stirring half an hour after a certain amount of TEA, completion of dropping is added dropwise under fair speed stirring, is then slowly added dropwise
Quantitative deionized water.This Waterborne Polyurethane Prepolymer is heated to 70 degree or so, a certain amount of butyl acrylate 3.0 is added
Gram, 0.3 gram of hydroxy-ethyl acrylate, 0.2 gram of the different cyanogen in heptan of azo two, 0.05 gram of lauryl mercaptan, stir a hour, then be warming up to 90
Degree, reacts half an hour, and cooling obtains the polyacrylate modified polyurethane aqueous emulsion of hydroxyl, particle diameter 100.1nm, pH value
7.2。
Embodiment 8 (component A preparation)
12 grams of OP-10,12 grams of lauryl sodium sulfate, 40 grams of water are well mixed, emulsifier solution is obtained.
By 24.6 grams of butyl acrylates, 32.3 grams of methyl methacrylates, 6.3 grams of octadecyl acrylates, 8.2 grams of acrylic acid
Hydroxyl ethyl ester, 2.9 grams of acrylic acid (polymerization inhibitor is evaporated off respectively in advance) are well mixed, and monomer mixture is made.
In four-hole boiling flask, 30 grams of water, the emulsifier solution of above-mentioned 1/3 amount, the monomer mixture of 1/3 amount, heating are added
To different 0.3 gram of the cyanogen in heptan of azo two is added at 80 DEG C, keep at this temperature, while above-mentioned 2/3 emulsifier solution, monomer is added dropwise
50 grams of mixture and water, are dripped off for 2-3 hours.Continue to cool after being incubated 1-2 hours at this temperature, nertralizer is filtered after neutralizing,
Obtain the acrylic acid ester emulsion of hydroxyl, particle diameter 132.0nm, pH value 7.0.
Embodiment 9 (component B preparation)
15.0 grams of HDI trimer (NCO content 22.4%), 24.0 grams of acetone are added into four-hole boiling flask, 40 are warming up to
DEG C, 5.44 grams of diacetylmonoxime is added portionwise, is finished in about 1 hour, keeps continuing to react at this temperature, tracking is until system NCO
Content reaches 1.61%, at this temperature, and drop in 3.2 grams of AAS salt (50% aqueous solution), half an hour is added dropwise and finishes, until infrared inspection
Survey no longer shows CNO groups peak, and add water emulsification 30 minutes at a high speed, obtained dispersion, and vacuum distillation sloughs solvent and produces component
B, particle diameter 75.8nm, pH value 7.2.
Embodiment 10 (component B preparation)
10.0 gram 0.05333 of HDI trimer (NCO content 22.4%), 15.0 grams of acetone are added into four-hole boiling flask, risen
Temperature is added portionwise 3,5- methylimidazoles 4.1 gram 0.0427, finished in about 1 hour to 35 DEG C, keeps continuing anti-at this temperature
Should, tracking reaches 1.53% up to system NCO content, at this temperature, and 2.0 grams of AAS salt (50% aqueous solution), half an hour is added dropwise
Interior drop finishes, until infrared detection no longer shows CNO groups peak, add water emulsification 30 minutes at a high speed, obtained dispersion, vacuum distillation
Slough solvent and produce component B, particle diameter 150.6nm, pH value 7.2.
Embodiment 11 (component B preparation)
3.88 grams of 14.6 grams of HDI and trimethylolpropane are added into four-hole boiling flask, acid dibutyl tin is added
0.05 gram, the 50 DEG C of reactions that heat up are added portionwise 5.5 grams of 3,5- methylimidazoles, added in about 1 hour to theoretical NCO content, after
The warm stirring reaction of continuation of insurance is cooled to 30 DEG C to theoretical NCO content, starts that 2.4 grams of 2,6- diaminocaproic acid sodium water solutions are added dropwise, about
Completion of dropping in half an hour, continues insulated and stirred half an hour, and add water emulsification 30 minutes at a high speed, obtained dispersion, vacuum distillation
Slough solvent and produce component B, particle diameter 70.6nm, pH value 7.2.
Embodiment 12 (component B preparation)
IPDI19.3 grams 0.08683 and 3.88 grams of trimethylolpropane are added into four-hole boiling flask, dibutyl two is added
2.8 grams of 3,5- methylimidazoles, about 1 hour is added portionwise to theoretical NCO content in 0.05 gram of month silicic acid tin, the 50 DEG C of reactions that heat up
Inside add, continue insulated and stirred and react to theoretical NCO content, add 1.7 grams of hexylene glycol, keep at a temperature of this, react to theory
CNO contents, are cooled to 30 DEG C, start that 4.4 grams of 6 hydroxycaproic acid sodium solutions, about completion of dropping in half an hour are added dropwise, and continue to be incubated
Half an hour is stirred, add water emulsification 30 minutes at a high speed, obtained dispersion, vacuum distillation sloughs solvent and produces component B, particle diameter
78.5nm, pH value 7.2.
Embodiment 13 (preparation of ink)
Each component (referring to table 1) in following formulas is added into beaker, mulser is emulsified 20-30 minutes (8000 at a high speed
Turn/min) after, mill base is added with rotating speed, continuing to emulsify 30 minutes, obtains paint ink, gained ink printed is knitted in pure cotton
Detected on thing, testing result is referring to table 2.
The ink list of ingredients of table 1
Table 2 prepares the physics and chemistry and stamp application test index of ink：
Note：In comparative example, component A is that sample prepared by example 2,8,12 accounts for ink ratio 20%.
The two-component adhesive of the present invention is can be seen that with respect to single group adhesive crock fastness raising 0.5- from upper table result
1 grade, solve the problem of current pigment digit printing crock fastness is not up to standard (3 grades of Conventional decal fastness to wet rubbing, dry friction jail
4 grades of degree, pigment digit printing ground zero, most of Printing is dry, fastness to wet rubbing does not reach Conventional decal level also, limits
Its development).
Claims (10)
1. a kind of aqueous dual-component adhesive for paint ink, it is characterised in that：Aqueous dual-component adhesive be component A and
Component B is constituted, by 3:4-20:1 mass ratio mixing；Wherein, component A is the aqueous polyurethane with amino or hydroxyl, carried
One kind or several in the water polyacrylic acid of amino or hydroxyl, the aqueous acrylic modified polyurethane with amino or hydroxyl
Kind, component B is aqueous blocked polyisocyanate.
2. the aqueous dual-component adhesive according to claim 1 for paint ink, it is characterised in that：It is described to carry ammonia
The aqueous polyurethane of base or hydroxyl is that soft segment polyester, diisocyanate, hydrophilic monomer, chain extender and crosslinking agent press 50-80:10-
30：2-6:0-3:React and obtain under 0-3 mass ratios.
3. the aqueous dual-component adhesive according to claim 2 for paint ink, it is characterised in that：The soft segment is gathered
Ester is one or more of mixing in polyester diol；Hydrophilic monomer is sulfonic group monomer, carboxylic acid group's monomer or polycyclic oxygen second
Alkane；Crosslinking agent is trihydroxylic alcohol, tertiary amine or tetraamine compound；Chain extender is C2-C8The dihydric alcohol or binary of straight or branched
Amine.
4. the aqueous dual-component adhesive according to claim 1 for paint ink, it is characterised in that：It is described to carry ammonia
The water polyacrylic acid of base or hydroxyl be polymerized monomer in the presence of emulsifying agent, through obtained by emulsion polymerization；Wherein, it polymerize single
Body is two or more in butyl acrylate, octadecyl acrylate, hydroxy-ethyl acrylate, methyl acrylate, acrylic acid.
5. the aqueous dual-component adhesive according to claim 1 for paint ink, it is characterised in that：It is described to carry ammonia
The aqueous acrylic modified polyurethane of base or hydroxyl is to be blocked with hydrophilic radical base polyurethane prepolymer for use as through hydroxy ethyl methacrylate
Afterwards, radical polymerization is carried out with acrylate monomer then to obtain by emulsifying.
6. the aqueous dual-component adhesive according to claim 1 for paint ink, it is characterised in that：The aqueous envelope
It is that blocked polyisocyanate dissipates acquisition through moisture to hold PIC；Wherein, blocked polyisocyanate is many by diisocyanate
Aggressiveness, hydrophilic monomer, end-capping reagent press 2.8-3:0.9-1.1:1.8-2.2 molar ratio reactions are obtained.
7. according to the aqueous dual-component adhesive for paint ink described in claim 1, it is characterised in that：The hydrophilic monomer
For sulfonic group monomer, carboxylic acid group's monomer or PEO；End-capping reagent is the end-capping reagent containing isocyano.
8. a kind of application of the aqueous dual-component adhesive for paint ink described in claim 1, it is characterised in that：It is described
Application of the adhesive in paint ink.
9. the application of the aqueous dual-component adhesive for paint ink as described in claim 8, it is characterised in that：Will bonding
Agent component A and B are well mixed according to the above ratio, are then added by the amount for accounting for ink gross mass 8-20% in mulser, then successively
By NMF, bactericide, cosolvent, pH value regulator, defoamer, surfactant and water, routinely ink set ratio adds
Enter, emulsify mixing in 20-30 minutes at a high speed under 8000-10000 turns/min revolutions after addition, be then to add face under this speed
Expect that mill base continues to emulsify 30-60 minutes, obtain paint ink.
10. the application of the aqueous dual-component adhesive for paint ink as described in claim 9, it is characterised in that：It is described
Paint ink acts on cotton using digital ink-jet mode, on polyester-cotton fabric after, be heat-treated fixation at 120-150 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107385963A (en) * | 2017-08-14 | 2017-11-24 | 东莞长联新材料科技股份有限公司 | Adhesive for pigment ink-jetting printing ink, the ink comprising it, preparation method and purposes |
| CN109054502A (en) * | 2018-10-24 | 2018-12-21 | 安徽金泽包装材料有限公司 | A kind of high glaze printing ink for cardboard |
| CN109403091A (en) * | 2018-10-30 | 2019-03-01 | 浙江蓝宇数码科技股份有限公司 | A kind of environment-friendly digital weaving inking printing pigment ink and preparation method |
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| CN112321176A (en) * | 2020-11-30 | 2021-02-05 | 天长市墨缘玻璃建材有限公司 | Artistic glass color fixing agent and using method thereof |
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| US11332633B2 (en) | 2018-04-16 | 2022-05-17 | Hewlett-Packard Development Company, L.P. | Textile printing |
| CN109054502A (en) * | 2018-10-24 | 2018-12-21 | 安徽金泽包装材料有限公司 | A kind of high glaze printing ink for cardboard |
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