CN106085172B - Bi-component waterborne colored paint based on water-soluble dyeing curing agent and preparation method thereof - Google Patents
Bi-component waterborne colored paint based on water-soluble dyeing curing agent and preparation method thereof Download PDFInfo
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- CN106085172B CN106085172B CN201610404294.3A CN201610404294A CN106085172B CN 106085172 B CN106085172 B CN 106085172B CN 201610404294 A CN201610404294 A CN 201610404294A CN 106085172 B CN106085172 B CN 106085172B
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- chromophore
- water
- curing agent
- chromo
- dyestuff
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 134
- 238000004043 dyeing Methods 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003973 paint Substances 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000002560 therapeutic procedure Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 74
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 8
- -1 tertiary amine ion Chemical class 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 101100412856 Mus musculus Rhod gene Proteins 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical class CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 229920002635 polyurethane Polymers 0.000 abstract description 7
- 239000003086 colorant Substances 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 26
- 239000002585 base Substances 0.000 description 22
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 230000000717 retained effect Effects 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YEOUFHBJWTZWCZ-UHFFFAOYSA-M sulforhodamine G Chemical compound [Na+].C=12C=C(C)C(NCC)=CC2=[O+]C=2C=C(NCC)C(C)=CC=2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O YEOUFHBJWTZWCZ-UHFFFAOYSA-M 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004214 Fast Green FCF Substances 0.000 description 1
- RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AHIBWURJLGCHAY-UHFFFAOYSA-N [S].C1=CC=CC=C1 Chemical compound [S].C1=CC=CC=C1 AHIBWURJLGCHAY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000019240 fast green FCF Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Coloring (AREA)
Abstract
The invention discloses a kind of preparation methods of the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent, it is characterized in first preparing water-soluble dyeing curing agent, then aqueous high molecular aqueous polyurethane, water soluble acrylic acid or aqueous epoxy resins are used as basic component, using water solubility dyeing curing agent as addO-on therapy, reaction is cured by certain mass proportioning, obtains the coloured aqueous coating of bi-component.The dyeing curing agent prepared using the method for the present invention has accomplished that curing, one step of dyeing carry out；Due to chromophore, chemistry is typed into high molecular strand after curing reaction, and chromophore publication is uniform, and not easy to migrate, color fastness and heat-resistant stability are good；Can also mix colours mechanism according to the three primary colors of color, and the color as needed for coating is cured after being mixed in a certain ratio red, green obtained, blue cured dose with aqueous high molecular again reacts, and easily obtains the bi-component waterborne coating of required color.
Description
Technical field
The invention belongs to aqueous high molecular technical field of coatings, and in particular to the synthesis and utilization of water solubility dyeing curing agent
Aqueous high molecular is cured to react to form coloured aqueous coating of bi-component and preparation method thereof with water solubility dyeing curing agent.
Background technology
Aqueous high molecular material, wherein aqueous polyurethane have short drying time, high-performance low VOC, appearance
Well, it the features such as solvent resistant, has broad application prospects；And water-and acrylate has excellent weatherability, resistance to acid and alkali etc.
A kind of feature, it has also become important coating.In the synthesis of aqueous high molecular material, since molecular chain structure is mostly linear or micro-
Crosslinking, the mechanical performance for leading to aqueous high molecular coating is not high, and water resistance is poor.It is carried in Chinese patent 201510132921.8
Go out, polyurethane curing agent is added in coating, the mechanical performance of film can be improved, improve its water resistance, weatherability.It is but this
Use of the curing agent in coloured aqueous polyurethane coating can lead to dyestuff difficulties in dispersion and dyestuff precipitation easy to migrate.Chinese patent
The synthetic method of aqueous polyurethane high molecular dye proposed in 201410554339.6, by parent containing amino or hydroxyl
Dyestuff is introduced into polyurethane chain, although solving the problems, such as dyeing firmness, its dye content is low and dyestuff utilization rate not
It is high.
Invention content
The purpose of the present invention is to propose to a kind of coloured aqueous coating of bi-component and its system based on water-soluble dyeing curing agent
Preparation Method, to solve, existing aqueous high molecular pigment dyeing firmness is low, dyestuff dispersion is uneven and poor heat-resistant stability asks
Topic.
The present invention includes：The preparation method of the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent；Wherein institute
Preparation has two or three or four or six-NCO as the aqueous high molecular of basis component and as addO-on therapy
The water-soluble dyeing series curing agent product of base and polyisocyanates containing chromophore；And it is contaminated using addO-on therapy water solubility
Color series curing agent product and basic components aqueous high molecular and deionized water and including antifoaming agent, wetting agent, thickener,
Auxiliary agent including auxiliary rheological agents and pH adjusting agent, the coloured painting of bi-component waterborne prepared according to requirements in required ratio
Expect series of products.
The preparation method of the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent of the present invention, including：By matter
Measure number using 100 parts as the aqueous high molecular of basic component and 6-12 parts of deionized waters, 0.5-1 parts of antifoaming agent, 1.0-2.0 parts
It is stirred evenly after wetting agent, 0.1-0.5 part thickener, 1.0-3.0 parts of auxiliary rheological agents and 0.1-0.3 parts of pH adjusting agent mixing；It stirs
It mixes the lower 2-10 parts of water-soluble dyeing curing agent as addO-on therapy of addition to be uniformly mixed, obtains bi-component waterborne colored paint；
It is characterized in that：The water-soluble dyeing curing agent is used with hydroxyl or amino and simultaneously with sodium sulfonate group or tertiary amine
The water-soluble dye and polyisocyanate curing agent of ion in molar ratio 1:1-2.2 being placed in reactor, add by polyisocyanate cyanogen
The solvent toluene of acid esters and dyestuff gross mass 50-80% and by polyisocyanates and the catalyst of dyestuff gross mass 0.1-0.8%
Dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, and vacuum distillation, washing and drying obtain having two or three
Or four or the water-soluble dyeing curing agent of six-NCO bases and the polyisocyanates containing chromophore；
The aqueous high molecular is selected from waterborne polyurethane resin, water-based acrylic resin or aqueous epoxy resins；
The water-soluble dyeing curing agent is with two, three, four or six-NCO bases and containing the more of chromophore
The water-soluble dyeing curing agent of isocyanates；
The antifoaming agent is selected from BYK-024, BYK-1660 of Bi Ke companies of Germany and the TEGO of Di Gao companies of Germany
It is one or more in foamex 810；
The wetting agent be selected from the BYK 346 of Bi Ke companies of Germany, BYK 348, Di Gao companies of Germany TEGO 440,
It is one or more in TEGO 450 and TEGO 482；
The thickener be selected from the ACRYSOL RM 8W of Rhom and Hass, ACRYSOL 12W, ACRYSOL5000 and
It is one or more in ACRYSOL RM2020NPR；
The auxiliary rheological agents are selected from BYK-420, BYK410, BYK-425, BYK-431, BYK-430 of Bi Ke companies of Germany
It is and one or more in the moral modest 2810 of this company of hamming；
The PH conditioning agents are selected from dimethyl amine, triethylamine, N, N- dimethylethanolamines, α-dihydroxymethyl ethamine, two
It is one or more in isopropanolamine and Pehanorm.
In the preparation method of the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent of the present invention, wherein institute
State the water-soluble of the polyisocyanates with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
Property dyeing curing agent in, there is two-NCO bases and the water-soluble dyeing curing agent containing chromophore, be by with monohydroxy
And dyestuff containing chromophore Chromo-I or with mono amino and dyestuff and three isocyanic acids containing chromophore Chromo-II
Ester reacts, and the chromophore in dyestuff is introduced into triisocyanate molecular structure, and obtained has two-NCO bases and contain
The water-soluble dyeing curing agent of chromophore Chromo-I or chromophore Chromo-II structures, concrete operation step are：
By 1:The amount of 1 molar ratio and by the dyestuff with monohydroxy and containing chromophore Chromo-I or with mono amino contain
There is the dyestuff of chromophore Chromo-II, be placed in reactor with triisocyanate；It adds by triisocyanate and the total matter of dyestuff
The toluene of 50-80% is measured as solvent, adds in the catalyst by triisocyanate and dyestuff gross mass 0.1-0.8% while stirring
Dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloromethane
Alkane washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-I or chromophore Chromo-
The water-soluble dyeing curing agent of II：
R in formula1For the agent structure in triisocyanate in addition to isocyanate groups.
The polyisocyanate cyanogen with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
In the water-soluble dyeing curing agent of acid esters, there are three tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is to pass through
Dyestuff with monohydroxy and containing chromophore Chromo-I or with mono amino and containing the dyestuff of chromophore Chromo-II,
It being reacted with tetraisocyanate, the chromophore in dyestuff is introduced into tetraisocyanate molecular structure, there are three obtained tools-
NCO bases and the water-soluble dyeing curing agent containing chromophore Chromo-I or chromophore Chromo-II structures, concrete operation step
For：
By 1:The amount of 1 molar ratio and by the dyestuff with monohydroxy and containing chromophore Chromo-I or with mono amino contain
There is the dyestuff of chromophore Chromo-II, be placed in reactor with tetraisocyanate；It adds by tetraisocyanate and the total matter of dyestuff
The toluene of 50-80% is measured as solvent, adds in the catalyst by tetraisocyanate and dyestuff gross mass 0.1-0.8% while stirring
Dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloromethane
Alkane washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-I or chromophore Chromo-
The water-soluble dyeing curing agent of II：
R in formula2For the agent structure in tetraisocyanate in addition to isocyanate groups.
The chromophore Chromo-I can be one of having structure, including：
Described as addO-on therapy have two or three or four or six-NCO bases and polyisocyanate containing chromophore
In the water-soluble dyeing curing agent of cyanate, there are four tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is logical
Cross the dyestuff with double hydroxyls and containing chromophore Chromo-III or with double amino and containing the dye of chromophore Chromo-IV
Material, reacts with triisocyanate, the chromophore in dyestuff is introduced into triisocyanate molecular structure, and obtained has four
A-NCO bases and the water-soluble dyeing curing agent containing chromophore Chromo-III or chromophore Chromo-IV structures, it is specific to grasp
It is as step：
By 1:The amount of 2-2.2 molar ratios is by the dyestuff with double hydroxyls and containing chromophore Chromo-III or with double ammonia
Base and containing the dyestuff of chromophore Chromo-IV, is placed in triisocyanate in reactor；It adds by triisocyanate and dye
The toluene of gross mass 50-80% is expected as solvent, adds in press triisocyanate and dyestuff gross mass 0.1-0.8% while stirring
Catalyst dibutyltin dilaurylate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or
Dichloromethane washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-III or chromophore
The water-soluble dyeing curing agent of Chromo-IV：
The polyisocyanate cyanogen with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
In the water-soluble dyeing curing agent of acid esters, there are six tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is to pass through
Dyestuff with double hydroxyls and containing chromophore Chromo-III with double amino and contains the dye of chromophore Chromo-IV
Material, reacts with tetraisocyanate, the chromophore in dyestuff is introduced into tetraisocyanate molecular structure, and obtained has six
A-NCO bases and the water-soluble dyeing curing agent containing chromophore Chromo-III or chromophore Chromo-IV structures, it is specific to grasp
It is as step：
By 1:The amount of 2-2.2 molar ratios is by the dyestuff with double hydroxyls and containing chromophore Chromo-III or with double ammonia
Base and containing the dyestuff of chromophore Chromo-IV, adds in tetraisocyanate in reactor；It adds by tetraisocyanate and dye
The toluene of gross mass 50-80% is expected as solvent, adds in press tetraisocyanate and dyestuff gross mass 0.1-0.8% while stirring
Catalyst dibutyltin dilaurylate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or
Dichloromethane washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-III or chromophore
The water-soluble dyeing curing agent of Chromo-IV：
The chromophore Chromo-III structures can be one of having structure, including：
The chromophore Chromo-IV structures can be one of having structure, including：
R in the reaction equation (a) or (c)1Structure can be one of having structure, including：
R in the reaction equation (b) or (d)2Structure is：
The preparation-obtained water-soluble dyeing curing agent of method using the present invention, by chromophore contained in molecular structure
Color can be divided into red, three kinds of green and blue；
It is listed with structural formula, wherein red water-soluble dyeing curing agent specifically includes：
Green water-soluble dyeing curing agent includes：
Blue water-soluble dyeing curing agent includes：
More than R in water-soluble dyeing curing agent structural formula1、R2Structure and the reaction equation (a) or (c), (b) or
(d) R in1、R2Structure is identical.
Using aqueous high molecular as basic component, preparation above-mentioned in the present invention had into two or three or four or six
The water-soluble dyeing series curing agent product of a-NCO bases and the polyisocyanates for containing chromophore is as addO-on therapy, with basis
Component uniformly mixes by a certain percentage, obtains the bi-component waterborne colored paint based on water-soluble dyeing curing agent of the present invention,
It can obtain respectively and the corresponding color of chromophore Chromo-I, Chromo-II, Chromo-III and Chromo-IV.
The water-soluble dyeing curing agent prepared using the present invention, can also be by reality according to the three primary colors toning mechanism of color
Obtained red, green, blue dyeing curing agent are mixed in a certain ratio by the color needed for bi-component waterborne colored paint
(can two components, also three components) be afterwards as addO-on therapy, then is uniformly mixed and be cured instead with basic components with certain proportion
It answers, the bi-component waterborne colored paint of required color can be obtained.
The present invention is taken through water-soluble dye and is reacted with polyisocyanates, first prepares water-soluble dyeing curing agent, should
The alternative conventional curing agent of curing agent is dyed, for waterborne polyurethane resin, water-based acrylic resin or water-base epoxy tree
While fat cures, can also corresponding water-base resin be given to assign the color needed, it is not necessary to reuse common aqueous by adding
The mode of pigment has accomplished that curing, one step of dyeing carry out to coloring resin.Due to chromophore, chemistry is keyed in after curing reaction
Into high molecular strand, chromophore publication is uniform, and not easy to migrate, color fastness and heat-resistant stability are good.The present invention uses water
Property macromolecule (aqueous polyurethane, water soluble acrylic acid or aqueous epoxy resins) be basic component, the water solubility prepared with the present invention
Dyeing curing agent is addO-on therapy, is cured reaction by certain mass proportioning, obtains the coloured aqueous coating of bi-component.It can also be according to
Mix colours mechanism according to the three primary colors of color, color as needed for coating by red, green obtained, blue cured dose by a certain percentage
It is cured and reacts with aqueous high molecular again after mixing, easily obtain the bi-component waterborne coating of required color.
Compared with prior art, the present invention has the following advantages：
1. since the present invention uses sodium sulfonate group or tertiary amine ion to make curing for the hydrophilic radical of polyisocyanate curing agent
Agent has good water dispersible, and curing performance is superior, and the curing open hour, cured film tensile strength was reachable more than 3 hours
42MPa；
2. there is the water-soluble dyeing curing agent of dyeing prepared by method using the present invention, after hardening due to
Chemistry is typed into high molecular strand chromophore, with the aqueous pigments or dyes of small molecule generally are directly mixed in aqueous height
The material obtained in molecule is compared, and chromophore publication can be made uniform using the method for the present invention, not easy to migrate, color fastness and heat-resisting steady
It is qualitative good；
3. water-soluble dyeing curing agent using the present invention, can as the color needed for coating by obtained red, green,
Blue cured dose be mixed in a certain ratio after be cured react with aqueous high molecular again, obtain needed for color bi-component waterborne
Coating；
4. water-soluble dyeing curing agent prepared by method using the present invention makes aqueous high molecular be sent out after curing due to carrying
The structure of color group belongs to the hard section of macromolecular chain, therefore can use the amount of curing agent or variety control aqueous high molecular by adjusting
The structure of chain hard section while color needed for acquisition, can play calorifics, mechanics of aqueous high molecular coating etc. after adjusting cures
Performance.
Description of the drawings
Fig. 1 is the fourier-transform infrared of water-soluble dyeing curing agent raw materials used in the embodiment of the present invention 1 and synthesis
Spectrum compares spectrogram.
Fig. 2 is the solid UV-Vis spectrograms of bi-component waterborne colored paint glued membrane prepared in the embodiment of the present invention 1.
Fig. 3 is the fourier-transform infrared of water-soluble dyeing curing agent raw materials used in the embodiment of the present invention 2 and synthesis
Spectrum compares spectrogram.
Fig. 4 is the fourier-transform infrared of water-soluble dyeing curing agent raw materials used in the embodiment of the present invention 3 and synthesis
Spectrum compares spectrogram.
Specific embodiment
Embodiment 1：
The 1- naphthols azo P-TOLUENE SULFO ACID 99 sodium (orange I), the HDI trimer of 3.59g and 3.42mL toluene of 2.34g are added in
In 25ml single-necked flasks；0.006g dibutyl tin laurates, the back flow reaction 6 under 130 DEG C of temperature conditions are added in while stirring
Hour；The system for the treatment of is cooled to room temperature, and toluene is sloughed with Rotary Evaporators；With dichloromethane washed product and in vacuum drying chamber
Drying is obtained to constant weight containing chromophore
Water-soluble dyeing curing agent D1.
100g waterborne polyurethane resins are added in the reactor of 250mL, are delayed under 500 revs/min of rotating speed uniform stirring
The slow 3g water solubilitys dyeing curing agent D1 that adds in is uniformly mixed, and obtains bi-component waterborne encrimson.The encrimson is placed in water
In the length and width of placing flat, the deep respectively groove type polytetrafluoroethylene (PTFE) template of 20cm, 20cm, 2cm, make breast at ambient temperature
Moisture slowly volatilizees in liquid, obtains the glued membrane of primary solidification；The glued membrane at a temperature of 60 DEG C is heat-treated 24 hours again, makes it solid
Change complete.The amount of the coating in template is added in by control, the thickness of solidified glue film that can make to finally obtain as needed is in 5-
Between 200 μm.Solid UV-Vis spectrogram of the present embodiment because needing measure bi-component waterborne colored paint, to avoid test by miscellaneous
Matter is interfered, therefore does not add in auxiliary agent.
Attached drawing 1 dyes the Fourier Transform Infrared Spectroscopy of curing agent D1 for the water solubility that the present embodiment is raw materials used and synthesizes
Compare spectrogram, spectrogram a, spectrogram b and spectrogram c are respectively the infrared spectrogram of orange I, HDI trimer, curing agent D1.Spectrogram exhibition
Show at the freedom-NH and hydrogen bonding-NH characteristic absorption peaks at 3433cm-1 and 3350cm-1,2942cm-1 and 2856cm-1
- CH3 and-CH2 characteristic absorption peaks ,-NCO the characteristic absorption peaks at 2275cm-1, the carbonyl of the carbamate at 1700cm-1
Sulfonic acid at base the characteristic absorption peak ,-CN characteristic absorption peaks of the carbamate at 1535cm-1,1175cm-1 and 1050cm-1
The characteristic absorption peak of naphthalene at base characteristic absorption peak and 758cm-1.The appearance of these characteristic absorption peaks shows orange I and HDI
Generation curing agent D1 after tripolymer reacts.
Fig. 2 is the solid UV-Vis spectrograms of bi-component waterborne colored paint glued membrane manufactured in the present embodiment, respectively at 466nm
With two larger absorption peaks of appearance at 534nm.Glued membrane shows beautiful orange red.
Respectively to cured film (the sample name of bi-component waterborne colored paint manufactured in the present embodiment：D1-PU) by GB/
T528-1998 carries out tensile strength and elongation at break, carries out wet rubbing color fastness detection, acquired results by QBT 2537-2001
As shown in the sample D1-PU in table 1.
Tensile strength, elongation at break and the wet rubbing color fastness of 1 bi-component waterborne colored paint cured glue film of table
Waterborne polyurethane resin basic components selected by the present embodiment are ten thousand China's chemistry6512 water-based hydroxyl polyurethanes
Dispersion, basic parameter are as shown in table 2.
2 aqueous high molecular basic components basic parameter of table
If the other conditions retained in the present embodiment are constant, orange I is changed into fixation green 50, fast green FCF or alkali blue
17, it can equally obtain water-soluble dyeing curing agent.
If the other conditions retained in the present embodiment are constant, HDI trimer is changed into HDI-TMP addition products or HDI contractings two
Urea can equally obtain water-soluble dyeing curing agent.
If the other conditions retained in the present embodiment are constant, and change basic components, and aqueous polyurethane dispersion is replaced
Water-based acrylic resin dispersion or aqueous epoxy resins dispersion are changed to, can equally obtain bi-component waterborne colored paint.
Embodiment 2：
The alkali blue 17 of 1.79g, the HDI trimer of 2.95g and 4.4mL toluene are added in 25ml single-necked flasks；While it stirs
It mixes side and adds in 0.038g dibutyl tin laurates, back flow reaction 5 hours under 90 DEG C of temperature conditions；The system for the treatment of is cooled to room
Temperature sloughs toluene with Rotary Evaporators；It dries to constant weight, is contained with dichloromethane washed product and in vacuum drying chamber
Chromophore
Water-soluble dyeing curing agent D2.
100g is added in the reactor of 250mL6512 water-based hydroxyl polyurethane dispersions, 1g antifoaming agent BYK-
024th, 2g wetting agents BYK 348,0.2gACRYSOLRM 8W, 2.0g auxiliary rheological agents BYK-420,0.1g Pehanorms and
10mL distilled water is slowly added to 1g water solubilitys dyeing curing agent D2 under 500 revs/min of rotating speed uniform stirring and is uniformly mixed, obtains
To bi-component waterborne blue paste.The blue paste is placed in horizontal positioned length and width, is deeply respectively 20cm, 20cm, 2cm
In groove type polytetrafluoroethylene (PTFE) template, moisture in lotion is made slowly to volatilize at ambient temperature, obtains the glued membrane of primary solidification；Again
The glued membrane at a temperature of 60 DEG C is heat-treated 24 hours, makes its completion of cure, obtains the solidified glue film that thickness is 5-200 μm.
Attached drawing 3 dyes the Fourier Transform Infrared Spectroscopy of curing agent D2 for the water solubility that the present embodiment is raw materials used and synthesizes
Compare spectrogram, spectrogram d, spectrogram e and spectrogram f be respectively alkali blue 17, HDI trimer, curing agent D2 infrared spectrogram.Spectrogram
Illustrate-CH3 at the freedom-NH and hydrogen bonding-NH characteristic absorption peaks at 3423cm-1,2929cm-1 and 2852cm-1 and-
CH2 the characteristic absorption peaks ,-NCO characteristic absorption peaks at 2262cm-1, the carbonyl characteristic absorption of the carbamate at 1679cm-1
The peak ,-CN characteristic absorption peaks of the carbamate at 1450cm-1, the characteristic absorption peak of the disubstituted benzenes ring at 1786cm-1；
C-N and C=N characteristic absorption peaks at 1351cm-1 and 1161cm-1；Quaternary ammonium salt characteristic absorption peak at 1623cm-1 and
- NH2 characteristic absorption vibration peaks at 1552cm-1.The appearance of these characteristic absorption peaks shows alkali blue 17 and HDI trimer
Curing agent D2 is generated after reacting.
Respectively to cured film (the sample name of bi-component waterborne colored paint manufactured in the present embodiment：D2-PU) by GB/
T528-1998 carries out tensile strength and elongation at break, carries out wet rubbing color fastness detection, acquired results by QBT 2537-2001
As shown in the sample D2-PU in table 1.
If the other conditions retained in the present embodiment are constant, BYK-024 is changed into BYK-1660 and TEGO foamex810
In it is one or more, can equally obtain bi-component waterborne colored paint.
If the other conditions retained in the present embodiment are constant, BYK 348 is changed into BYK 346, TEGO 440, TEGO450
With one or more in TEGO 482, bi-component waterborne colored paint can be equally obtained.
If the other conditions retained in the present embodiment are constant, ACRYSOLRM 8W are changed into ACRYSOL 12W, ACRYSOL
5000 with one or more in ACRYSOL RM2020NPR, can equally obtain bi-component waterborne colored paint.
If the other conditions retained in the present embodiment are constant, by BYK-420 change into BYK410, moral modest 2810, BYK-425,
BYK-431 can equally obtain bi-component waterborne colored paint with one or more in BYK-430.
If the other conditions retained in the present embodiment are constant, Pehanorm is changed into dimethyl amine, triethylamine, N,
It is one or more in N- dimethylethanolamines, α-dihydroxymethyl ethamine, diisopropanolamine (DIPA), it can equally obtain bi-component waterborne
Colored paint.
If the other conditions retained in the present embodiment are constant, alkali blue 17 is changed into 4- [(4- aminophenyls) azo] benzene sulphur
Sour mono-sodium salt can equally obtain corresponding water-soluble dyeing curing agent and bi-component waterborne colored paint.
Embodiment 3：
The acid red 50 of 1.56g, the HDI trimer of 2.85g and 3.05mL toluene are added in 25ml single-necked flasks；While it stirs
It mixes side and adds in 0.022g dibutyl tin laurates, back flow reaction 4 hours under 130 DEG C of temperature conditions；The system for the treatment of is cooled to room
Temperature sloughs toluene with Rotary Evaporators；It dries to constant weight, is contained with dichloromethane washed product and in vacuum drying chamber
Chromophore
Water-soluble dyeing curing agent D3.
100g is added in the reactor of 250mL6512 water-based hydroxyl polyurethane dispersions, 1g antifoaming agent BYK-
1660th, 2g wetting agents BYK 346,0.2gACRYSOL 12W, 2.0g auxiliary rheological agents BYK-410,0.1g α-dihydroxymethyl ethamine and
8mL distilled water is slowly added to 4.8g water solubilitys dyeing curing agent D3 under 500 revs/min of rotating speed uniform stirring and is uniformly mixed, obtains
To bi-component waterborne encrimson.The encrimson is placed in horizontal positioned length and width, is deeply respectively 20cm, 20cm, 2cm
In groove type polytetrafluoroethylene (PTFE) template, moisture in lotion is made slowly to volatilize at ambient temperature, obtains the glued membrane of primary solidification；Again
The glued membrane at a temperature of 60 DEG C is heat-treated 24 hours, makes its completion of cure, obtains the solidified glue film that thickness is 5-200 μm.
Attached drawing 4 dyes the Fourier Transform Infrared Spectroscopy of curing agent D3 for the water solubility that the present embodiment is raw materials used and synthesizes
Compare spectrogram, spectrogram g, spectrogram h and spectrogram i are respectively the infrared spectrogram of acid red 50, HDI trimer, curing agent D3.Spectrogram
Illustrate-CH3 at the freedom-NH and hydrogen bonding-NH characteristic absorption peaks at 3424cm-1,2945m-1 and 2858cm-1 and-
CH2 the characteristic absorption peaks ,-NCO characteristic absorption peaks at 2266cm-1, the carbonyl characteristic absorption of the carbamate at 1693cm-1
The peak ,-CN characteristic absorption peaks of carbamate at 1458cm-1 and the phenyl ring skeleton at 1550cm-1 and 1360cm-1 shake
Dynamic characteristic absorption peak.The appearance of these characteristic absorption peaks, which shows to generate after acid red 50 reacts with HDI trimer, to be cured
Agent D3.
Respectively to cured film (the sample name of bi-component waterborne colored paint manufactured in the present embodiment：D3-PU) by GB/
T528-1998 carries out tensile strength and elongation at break, carries out wet rubbing color fastness detection, acquired results by QBT 2537-2001
As shown in the sample D3-PU in table 1.
If the other conditions retained in the present embodiment are constant, acid red 50 is changed into acid green A, can equally obtain corresponding
Water-soluble dyeing curing agent and bi-component waterborne colored paint.
If the other conditions retained in the present embodiment are constant, HDI trimer is changed into HDI-TMP addition products, HDI biurets
Or hydrophilic modifying HDI trimer, it can equally obtain corresponding water-soluble dyeing curing agent and bi-component waterborne colored paint.
Embodiment 4：
The acid mordant navy blue of 1.56g, the HDI trimer of 3.82g and 4.35mL toluene are added in 25ml single-necked flasks；
0.022g dibutyl tin laurates, back flow reaction 5 hours under 100 DEG C of temperature conditions are added in while stirring；Treat that system cools down
To room temperature, toluene is sloughed with Rotary Evaporators；It dries to constant weight, obtains with dichloromethane washed product and in vacuum drying chamber
Contain chromophore
Water-soluble dyeing curing agent D4.
100g water-based acrylic resins, 1g antifoaming agent BYK-024,2g wetting agents TEGO are added in the reactor of 250mL
440th, 0.2gACRYSOL 5000,2.0g auxiliary rheological agents morals be modest 2810,0.1g α-dihydroxymethyl ethamine and 9mL distilled water, 500
Rev/min rotating speed uniform stirring under be slowly added to 2.3g water solubilitys dyeing curing agent D4 be uniformly mixed, obtain bi-component waterborne indigo plant
Color coating.The blue paste is placed in the groove type polytetrafluoroethyl-ne of horizontal positioned length and width, deep respectively 20cm, 20cm, 2cm
In alkene template, moisture in lotion is made slowly to volatilize at ambient temperature, obtains the glued membrane of primary solidification；Again by the glued membrane at 60 DEG C
At a temperature of be heat-treated 24 hours, make its completion of cure, it is 5-200 μm of solidified glue film to obtain thickness.
Respectively to cured film (the sample name of bi-component waterborne colored paint manufactured in the present embodiment：D4-PA) by GB/
T528-1998 carries out tensile strength and elongation at break, carries out wet rubbing color fastness detection, acquired results by QBT 2537-2001
As shown in the sample D4-PA in table 1.
Water-borne acrylic resin-based plinth component selected by the present embodiment is ten thousand China's chemistry2042 hydroxy acrylic acids disperse
Body, basic parameter are as shown in table 2.
If the other conditions retained in the present embodiment are constant, change acid mordant navy blue into acid green 28, can equally obtain
To corresponding water-soluble dyeing curing agent and bi-component waterborne colored paint.
If the other conditions retained in the present embodiment are constant, HDI trimer is changed into HDI-TMP addition products, HDI biurets
Or hydrophilic modifying HDI trimer, it can equally obtain corresponding water-soluble dyeing curing agent and bi-component waterborne colored paint.
Embodiment 5：
100g is added in the reactor of 250mL2042 hydroxyl acrylic aqueous dispersions, 1g antifoaming agent BYK-024,
2g wetting agents TEGO 440,0.2gACRYSOL 5000,2.0g auxiliary rheological agents morals are modest 2810,0.1g α-dihydroxymethyl ethamine and
It is water-soluble to be slowly added to 1.0g water solubilitys dyeing curing agent D3 and 1.5g under 500 revs/min of rotating speed uniform stirring for 9mL distilled water
Property dyeing curing agent D2 be uniformly mixed, obtain bi-component waterborne purple paint.By the purple paint be placed in horizontal positioned length,
In wide, the deep respectively groove type polytetrafluoroethylene (PTFE) template of 20cm, 20cm, 2cm, make moisture in lotion slow at ambient temperature
Volatilization obtains the glued membrane of primary solidification；The glued membrane at a temperature of 60 DEG C is heat-treated 24 hours again, makes its completion of cure, obtains
Thickness is 5-200 μm of solidified glue film.
Claims (6)
1. a kind of preparation method of the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent, including：By mass fraction
Using 100 parts of aqueous high moleculars as basic component and 6-12 parts of deionized waters, 0.5-1 parts of antifoaming agent, 1.0-2.0 parts of wettings
It is stirred evenly after agent, 0.1-0.5 parts of thickeners, 1.0-3.0 parts of auxiliary rheological agents and 0.1-0.3 parts of pH adjusting agent mixing；Under stirring
It adds in the 2-10 parts of water-soluble dyeing curing agent as addO-on therapy to be uniformly mixed, obtains bi-component waterborne colored paint；It is special
Sign is：The water-soluble dyeing curing agent is used with hydroxyl or amino and simultaneously with sodium sulfonate group or tertiary amine ion
Water-soluble dye and polyisocyanate curing agent in molar ratio 1:1-2.2 is placed in reactor, is added by polyisocyanates
With the solvent toluene of dyestuff gross mass 50-80% and by polyisocyanates and the catalyst dibutyltin of dyestuff gross mass 0.1-0.8%
Dilaurylate reacts 4-6 hours at 80-130 DEG C, and vacuum distillation, washing and drying obtain having two or three or four
The water-soluble dyeing curing agent of a or six-NCO bases and the polyisocyanates containing chromophore；
The aqueous high molecular is selected from waterborne polyurethane resin, water-based acrylic resin or aqueous epoxy resins；
The water-soluble dyeing curing agent is that have two, three, four or six-NCO bases and the polyisocyanate cyanogen containing chromophore
The water-soluble dyeing curing agent of acid esters；
The antifoaming agent is selected from BYK-024, BYK-1660 of Bi Ke companies of Germany and the TEGO foamex of Di Gao companies of Germany
It is one or more in 810；
The wetting agent be selected from the BYK 346 of Bi Ke companies of Germany, BYK 348, Di Gao companies of Germany TEGO 440, TEGO
It is one or more in 450 and TEGO 482；
The thickener be selected from the ACRYSOL RM 8W of Rhom and Hass, ACRYSOL 12W, ACRYSOL 5000 and
It is one or more in ACRYSOLRM2020NPR；
The auxiliary rheological agents be selected from Bi Ke companies of Germany BYK-420, BYK410, BYK-425, BYK-431, BYK-430 and
It is one or more in the moral modest 2810 of this company of hamming；
The pH conditioning agents are selected from dimethyl amine, triethylamine, N, N- dimethylethanolamines, α-dihydroxymethyl ethamine, diisopropyl
It is one or more in hydramine and Pehanorm.
2. the preparation method of the coloured aqueous coating of bi-component as described in claim 1 based on water-soluble dyeing curing agent, feature
It is the polyisocyanates with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
Water-soluble dyeing curing agent in, there is two-NCO bases and the water-soluble dyeing curing agent containing chromophore, be by having
Monohydroxy and dyestuff containing chromophore Chromo-I or with mono amino and the dyestuff containing chromophore Chromo-II and three
Isocyanates reacts, and the chromophore in dyestuff is introduced into triisocyanate molecular structure, and obtained has two-NCO bases
And the water-soluble dyeing curing agent containing chromophore Chromo-I or chromophore Chromo-II structures, concrete operation step are：
By 1:The amount of 1 molar ratio by the dyestuff with monohydroxy and containing chromophore Chromo-I or with mono amino and containing hair
The dyestuff of color group Chromo-II, is placed in triisocyanate in reactor；It adds by triisocyanate and dyestuff gross mass
The toluene of 50-80% adds in the catalyst two by triisocyanate and dyestuff gross mass 0.1-0.8% while stirring as solvent
Dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloromethane
Washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-I or chromophore Chromo-II
Water-soluble dyeing curing agent：
R in formula1For the agent structure in triisocyanate in addition to isocyanate groups.
3. the preparation method of the coloured aqueous coating of bi-component as described in claim 1 based on water-soluble dyeing curing agent, feature
It is the polyisocyanates with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
Water-soluble dyeing curing agent in, there are three tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is by having
Monohydroxy and dyestuff containing chromophore Chromo-I or with mono amino and containing the dyestuff of chromophore Chromo-II, with four
Isocyanates reacts, and the chromophore in dyestuff is introduced into tetraisocyanate molecular structure, there are three obtained tools-NCO bases
And the water-soluble dyeing curing agent containing chromophore Chromo-I or chromophore Chromo-II structures, concrete operation step are：
By 1:The amount of 1 molar ratio by the dyestuff with monohydroxy and containing chromophore Chromo-I or with mono amino and containing hair
The dyestuff of color group Chromo-II, is placed in tetraisocyanate in reactor；It adds by tetraisocyanate and dyestuff gross mass
The toluene of 50-80% adds in the catalyst two by tetraisocyanate and dyestuff gross mass 0.1-0.8% while stirring as solvent
Dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloromethane
Washed product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-I or chromophore Chromo-II
Water-soluble dyeing curing agent：
R in formula2For the agent structure in tetraisocyanate in addition to isocyanate groups；
The chromophore Chromo-I is：
Chromophore Chromo-II structures in the reaction equation are：
4. the preparation method of the coloured aqueous coating of bi-component as described in claim 1 based on water-soluble dyeing curing agent, feature
Being described as addO-on therapy has two or three or four or six-NCO bases and polyisocyanic acid containing chromophore
In the water-soluble dyeing curing agent of ester, there are four tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is to pass through tool
There are double hydroxyls and a dyestuff containing chromophore Chromo-III or with double amino and containing the dyestuff of chromophore Chromo-IV,
It being reacted with triisocyanate, the chromophore in dyestuff is introduced into triisocyanate molecular structure, there are four obtained tools-
NCO bases and the water-soluble dyeing curing agent containing chromophore Chromo-III or chromophore Chromo-IV structures, concrete operations step
Suddenly it is：
By 1:The amount of 2-2.2 molar ratios by the dyestuff with double hydroxyls and containing chromophore Chromo-III or with double amino simultaneously
Dyestuff containing chromophore Chromo-IV, is placed in triisocyanate in reactor；It adds total by triisocyanate and dyestuff
The toluene of quality 50-80% adds in the catalysis by triisocyanate and dyestuff gross mass 0.1-0.8% while stirring as solvent
Agent dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloro
Methane wash product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-III or chromophore
The water-soluble dyeing curing agent of Chromo-IV：
5. the preparation method of the coloured aqueous coating of bi-component as described in claim 1 based on water-soluble dyeing curing agent, feature
It is the polyisocyanates with two, three, four or six-NCO bases and containing chromophore as addO-on therapy
Water-soluble dyeing curing agent in, there are six tools-NCO bases and the water-soluble dyeing curing agent containing chromophore is by having
Double hydroxyls and dyestuff containing chromophore Chromo-III or with double amino and containing the dyestuff of chromophore Chromo-IV, with
Tetraisocyanate reacts, and the chromophore in dyestuff is introduced into tetraisocyanate molecular structure, there are six obtained tools-NCO
Base and the water-soluble dyeing curing agent containing chromophore Chromo-III or chromophore Chromo-IV structures, concrete operation step
For：
By 1:The amount of 2-2.2 molar ratios by the dyestuff with double hydroxyls and containing chromophore Chromo-III or with double amino simultaneously
Dyestuff containing chromophore Chromo-IV is added in tetraisocyanate in reactor；It adds total by tetraisocyanate and dyestuff
The toluene of quality 50-80% adds in the catalysis by tetraisocyanate and dyestuff gross mass 0.1-0.8% while stirring as solvent
Agent dibutyl tin laurate reacts 4-6 hours at 80-130 DEG C, vacuum distillation removing solvent after cooling；With acetone or dichloro
Methane wash product is simultaneously dried in vacuum drying chamber to constant weight to get to containing chromophore Chromo-III or chromophore
The water-soluble dyeing curing agent of Chromo-IV：
The chromophore Chromo-III structures are：
The chromophore Chromo-IV structures are：
R in reaction equation1Structure is：
R in reaction equation2Structure is：
6. the coloured aqueous coating of bi-component based on water-soluble dyeing curing agent prepared by claim 1 the method, feature
It is that the water-soluble dyeing curing agent is divided into red, three kinds of green and blue by chromophore colour contained in molecular structure,
Wherein red water-soluble dyeing curing agent includes：
Green water-soluble dyeing curing agent includes：
Blue water-soluble dyeing curing agent includes：
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