CN1827713A - Casein type aqueous ink and method for preparing same - Google Patents
Casein type aqueous ink and method for preparing same Download PDFInfo
- Publication number
- CN1827713A CN1827713A CN 200610034699 CN200610034699A CN1827713A CN 1827713 A CN1827713 A CN 1827713A CN 200610034699 CN200610034699 CN 200610034699 CN 200610034699 A CN200610034699 A CN 200610034699A CN 1827713 A CN1827713 A CN 1827713A
- Authority
- CN
- China
- Prior art keywords
- water
- casein
- preparation
- aqueous ink
- clay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000005018 casein Substances 0.000 title claims abstract description 55
- 235000021240 caseins Nutrition 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000004927 clay Substances 0.000 claims abstract description 48
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000002687 intercalation Effects 0.000 claims abstract description 30
- 238000009830 intercalation Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000000049 pigment Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 150000002009 diols Chemical class 0.000 claims abstract description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 39
- 235000013305 food Nutrition 0.000 claims description 36
- 239000003112 inhibitor Substances 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical group O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 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 9
- 239000002253 acid Substances 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 230000000176 photostabilization Effects 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000003429 antifungal agent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 235000013351 cheese Nutrition 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 74
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000001054 red pigment Substances 0.000 description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000001055 blue pigment Substances 0.000 description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 4
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 101100138712 Schizosaccharomyces pombe (strain 972 / ATCC 24843) puc1 gene Proteins 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DEHKKLGPRZMWMW-UHFFFAOYSA-N C=CC1=CC=CC=C1.NC#N Chemical compound C=CC1=CC=CC=C1.NC#N DEHKKLGPRZMWMW-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical class [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a cheese water-type ink and its process for preparing. The method is as follows: polymerizing arbowax or polyester diol, dimethylol propionic acid and isophorone diisocyanate under accelerating effect of catalyst, stopping heating after 3-5 hours; adding triethylamine to neutralize after cooling, and adding water to prepare polymer solution with 20-40 % of solid content, adding drainable clay, stirring to obtain clay intercalation polyurethane, dissolving dry casein into the water in alkali condition, preparing to obtain aqueous solution of dry casein with 10-20 % of solid content; mixing intercalation polyurethane with aqueous solution of dry casein evenly to produce junction material of water-type ink, and adding pigments, alcohol, anti-fungus agent and water, grinding, adjusting viscosity to obtain water-type ink. The invention selects renewable natural resources as its main film forming matter, so it is environment-friendly and can save energy; the said water-type ink is of simple process and reasonable cost; and the quality of the obtained ink meets the requirement of the decorative laminate printing.
Description
Technical field
The present invention relates to water color ink, particularly a kind of is main water color ink that connects material and preparation method thereof with the modified casein.
Background technology
Water color ink has the environmental protection characteristics, progressively replaces solvent type ink in the modern packaging printing.Soluble acrylic ester emulsion is the water color ink material that connects commonly used in the buck, the solvability of connection material is similar to the multipolymer in the organic solvent system printing ink in buck, therefore meet high speed printing to connecting material is dissolved (solubility) repeatedly by former China ink in version roller, mesh and transfer process requirement, be used widely in practice.But existing when using in intaglio printing decorative paper printing ink films, and to add man-hour at 150～190 ℃ easily anti-sticking, inhales the glue quantity not sufficient and defective such as easy decolouring when trimeric cyanamide soaks.
Casein food grade is a natural polymer, is usually used in hide finishes and tackiness agent, has fast drying, adhesive capacity is strong, film forming is water-fast, characteristics such as high temperature resistant, and particularly the casein food grade film forming is more loose, and trimeric cyanamide easily sees through, and meets the requirement of decorative paper post-treatment.But because decorative paper printing equipment speed is fast, last machine oil China ink solid content is lower, and casein food grade needs thickening, adhesiveness increasing and modifying during low-solid content.Urethane is adhesives preferably, and aqueous polyurethane associates in water can increase the solution denseness, but resistant polyurethane is hot poor, is not suitable for using under the hot conditions.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of casein type decorative paper water-based printing ink.
Another object of the present invention is to provide the preparation method of above-mentioned water color ink.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of casein type aqueous ink comprises following processing step and processing condition:
(1) in solvent, add polyoxyethylene glycol or polyester diol, dimethylol propionic acid (DMPA), isophorone diisocyanate (IPDI), be warming up to 80～90 ℃, add the catalyzer di-n-butyltin dilaurate, carry out polyreaction, stop heating after 3～5 hours; Be cooled to 50～60 ℃, add triethylamine (TEA) neutralization, and adding entry, to be made into solid content be 20～40% polymers soln, in polymers soln, add the hydrophobic type clay, making clay weight concentration in solution is 1～6%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), described reactive group isocyanate group and hydroxyl (NCO with-OH) mol ratio is 1.1～1.5: 1, described dimethylol propionic acid provides the hydroxyl mole number to account for 5～20% of total overall reaction thing hydroxyl mole number, and described dimethylol propionic acid mole number equates with the triethylamine mole number.
(2) under alkaline condition that casein food grade is water-soluble, preparation obtains the casein food grade aqueous solution of solid content 10～20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material, in water color ink connection material, add pigment, ethanol, mould inhibitor and water, be ground to fineness 5～10 μ, transfer viscosity to 30～50 second (Zahn 3# cup, survey ink viscosity with pricking the grace cup), obtain water color ink.Described intercalation urethane accounts for and connects 5～20% of material weight percent, and described water color ink connects material, pigment, ethanol, mould inhibitor and water by weight, and water color ink connects 50～70 parts in material, 10～20 parts of pigment, 5～15 parts of ethanol, 0.1～0.5 part of mould inhibitor, 5～35 parts in water.
In order to realize the present invention better, solvent comprises acetone, pyrrolidone or vinyl acetic monomer etc. in the described step (1); Preferred polyoxyethylene glycol is the polyoxyethylene glycol of molecular weight 400～600, and the preferred polyester dibasic alcohol is the poly-hexanodioic acid caprolactone dibasic alcohol of weight-average molecular weight 500～2000 or the own ester dibasic alcohol of hexanodioic acid of weight-average molecular weight 500～2000.Described step (2) neutral and alkali condition is a pH value 7.5～8.5.
In the described step (3) pigment can for red, yellow, blue, deceive or pigment of all kinds such as green, described pigment photostabilization is 6～8 grades; Described mould inhibitor is an isothiazolinone.
A kind of casein type aqueous ink is prepared from by above-mentioned preparation method.
Casein type aqueous ink of the present invention can be used for the intaglio printing of decorative paper.It is the adhering resin of printing ink that the present invention adopts natural polymer one casein food grade, by clay intercalated polyurethane-modified, makes it meet the requirement of decorative paper printing-ink.
Principle of the present invention is to have utilized casein food grade can form the characteristics of loose porous film, improve the denseness of casein food grade dilute solution with clay intercalated urethane, obtain to be used for the intaglio plate high speed printing, film and can satisfy required high temperature resistant, the anti-trimeric cyanamide (vinylbenzene) of decorative paper post-treatment and inhale the glue amount water color ink that requires such as big.
The present invention compared with prior art has following advantage and beneficial effect: the present invention is main film forming matter with natural reproducible resource, has environmental protection and energy saving; The preparation method is simple for this water color ink, and cost is reasonable; Ink quality meets the decorative paper print request.It is after connecting the printing ink film forming of material that the present invention adopts modified casein, is coated with film heat resistance, suction glue amount, anti-trimeric cyanamide and vinylbenzene performance and all is better than the solvable acrylic resin printing ink of alkali commonly used, is applicable to the post-treatment of decorative paper.Hot and the solution denseness of resistant polyurethane behind the intercalation clay of the present invention all is significantly improved, and adopts the urethane and the casein food grade of clay alteration solution combined, obtains filming of improved performance, can be applicable to the decorative paper printing.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as (not being called performed polymer before the aquation), the solvent acetone mass percent is 30% in the performed polymer.In solvent acetone, add PEG400 (polyoxyethylene glycol), dimethylol propionic acid (DMPA), isophorone diisocyanate (IPDI), be warming up to 90 ℃, add 2 of di-n-butyltin dilaurates of catalyzer (0.05ml), carry out polyreaction, 3.5 stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after hour, make base polyurethane prepolymer for use as; Be cooled to 50 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 40% polymers soln, be brown heavy-gravity liquid (PU-1), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 1%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 5% of total overall reaction thing hydroxyl mole number.
(2) (pH value 7.5) is water-soluble with casein food grade under alkaline condition, and preparation obtains the casein food grade aqueous solution of solid content 20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC1), wherein intercalation urethane accounts for and connects material weight percent 20%, connect adding yellow ultramarine PY86 (the yellow ultramarine photostabilization is 7 grades), ethanol, mould inhibitor, water in the material at water color ink, be ground to fineness 10 μ, transfer viscosity to 30 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, yellow ultramarine, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 65 parts in material, 12 parts of yellow ultramarines, 15 parts of ethanol, 0.3 part of mould inhibitor isothiazolinone, 12.7 parts in water.
Embodiment 2
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as, solvent pyrrolidone mass percent is 30% in the performed polymer.In the solvent pyrrolidone, add PEG600 (polyoxyethylene glycol), dimethylol propionic acid (DMPA), isophorone diisocyanate (IPDI), be warming up to 80～90 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3 hours, make base polyurethane prepolymer for use as; Be cooled to 60 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 40% polymers soln, be brown heavy-gravity liquid (PU-2), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 2%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 20% of total overall reaction thing hydroxyl mole number.
(2) (pH value 8.5) is water-soluble with casein food grade under alkaline condition, and preparation obtains the casein food grade aqueous solution of solid content 20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC2), wherein intercalation urethane accounts for and connects 5% of material weight percent, connect adding red pigment PR185 (the red pigment photostabilization is 6 grades), ethanol, mould inhibitor, water in the material at water color ink, be ground to fineness 10 μ, transfer viscosity to 50 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, red pigment, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 70 parts in material, 15 parts of red pigments, 10 parts of ethanol, 0.2 part of mould inhibitor isothiazolinone, 4.8 parts in water.
Embodiment 3
(1) synthetic-NCO with-the OH mol ratio is 1.3: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In the solvent vinyl acetic monomer, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 500, be warming up to 80 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, 3.5 stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after hour, make base polyurethane prepolymer for use as; Be cooled to 55 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 30% polymers soln, be brown heavy-gravity liquid (PU-3), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 2%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.3: 1, DMPA provides the hydroxyl mole number to account for 15% of total overall reaction thing hydroxyl mole number.
(2) (pH value 8.0) is water-soluble with casein food grade under weak basic condition, and preparation obtains the casein food grade aqueous solution of solid content 15%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC3), wherein intercalation urethane accounts for and connects 10% of material weight percent, in water color ink connection material, add blue pigments (the blue pigments photostabilization is 8 grades), ethanol, mould inhibitor, water, be ground to fineness 5 μ, transfer viscosity to 40 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, blue pigments, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 50 parts in material, 20 parts of blue pigmentss, 5 parts of ethanol, 0.5 part of mould inhibitor isothiazolinone, 5 parts in water.
Embodiment 4
(1) synthetic-NCO with-the OH mol ratio is 1.4: 1 a base polyurethane prepolymer for use as, the solvent acetone mass percent is 30% in the performed polymer.In solvent acetone, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 1000, be warming up to 80 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, 4.5 stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after hour, make base polyurethane prepolymer for use as; Be cooled to 55 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 20% polymers soln, be brown heavy-gravity liquid (PU-4), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 2%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.4: 1, DMPA provides the hydroxyl mole number to account for 20% of total overall reaction thing hydroxyl mole number.
(2) (pH value 8.5) is water-soluble with casein food grade under alkaline condition, and preparation obtains the casein food grade aqueous solution of solid content 20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC4), wherein intercalation urethane accounts for and connects 15% of material weight percent, in water color ink connection material, add red pigment (the red pigment photostabilization is 6 grades), ethanol, mould inhibitor, water, be ground to fineness 10 μ, transfer viscosity to 50 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, red pigment, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 55 parts in material, 15 parts of red pigments, 5 parts of ethanol, 0.1 part of mould inhibitor isothiazolinone, 25 parts in water.
Embodiment 5
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In the solvent vinyl acetic monomer, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 500, be warming up to 85 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3 hours, make base polyurethane prepolymer for use as; Be cooled to 60 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 30% polymers soln, be brown heavy-gravity liquid (PU-5), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 4%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 15% of total overall reaction thing hydroxyl mole number.
(2) (pH value 7.5) is water-soluble with casein food grade under weak basic condition, and preparation obtains the casein food grade aqueous solution of solid content 20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC5), wherein intercalation urethane accounts for and connects 20% of material weight percent, in water color ink connection material, add blue pigments (the blue pigments photostabilization is 8 grades), ethanol, mould inhibitor, water, be ground to fineness 10 μ, transfer viscosity to 35 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, blue pigments, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 60 parts in material, 15 parts of blue pigmentss, 10 parts of ethanol, 0.5 part of mould inhibitor isothiazolinone, 15 parts in water.
Embodiment 6
(1) synthetic-NCO with-the OH mol ratio is 1.3: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In the solvent vinyl acetic monomer, the poly-hexanodioic acid caprolactone dibasic alcohol, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 2000, be warming up to 90 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3 hours, make base polyurethane prepolymer for use as; Be cooled to 50 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 35% polymers soln, be brown heavy-gravity liquid (PU-6), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 4%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.3: 1, DMPA provides the hydroxyl mole number to account for 12% of total overall reaction thing hydroxyl mole number.
(2) (pH value 8.0) is water-soluble with casein food grade under alkaline condition, and preparation obtains the casein food grade aqueous solution of solid content 20%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC6), wherein intercalation urethane accounts for and connects 12% of material weight percent, in water color ink connection material, add veridian (the veridian photostabilization is 7 grades), ethanol, mould inhibitor, water, be ground to fineness 6 μ, transfer viscosity to 45 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, veridian, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 50 parts in material, 10 parts of veridians, 5 parts of ethanol, 0.1 part of mould inhibitor isothiazolinone, 35 parts in water.
Embodiment 7
(1) synthetic-NCO with-the OH mol ratio is 1.5: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In the solvent vinyl acetic monomer, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 500, be warming up to 80 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 5 hours, make base polyurethane prepolymer for use as; Be cooled to 60 ℃, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization, and adding entry, to be made into solid content be 30% polymers soln, be brown heavy-gravity liquid (PU-7), in polymers soln, add hydrophobic type clay (clay (Clay tone II), U.S. Laporte company), making clay weight concentration in solution is 6%, stirring obtains clay intercalated urethane (being called for short intercalation urethane), wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.5: 1, DMPA provides the hydroxyl mole number to account for 10% of total overall reaction thing hydroxyl mole number.
(2) (pH value 7.5) is water-soluble with casein food grade under weak basic condition, and preparation obtains the casein food grade aqueous solution of solid content 10%.
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material (PUC7), wherein intercalation urethane accounts for and connects 10% of material weight percent, in water color ink connection material, add black pigment (the black pigment photostabilization is 8 grades), ethanol, mould inhibitor, water, be ground to fineness 8 μ, transfer viscosity to 50 second (Zahn 3# cup is surveyed ink viscosity with pricking the grace cup), obtain water color ink.Described water color ink connects material, black pigment, ethanol, mould inhibitor isothiazolinone, water by weight, and water color ink connects 60 parts in material, 20 parts of black pigments, 15 parts of ethanol, 0.5 part of mould inhibitor isothiazolinone, 5 parts in water.
The cooperation table of table 1 urethane
| Sample number | Clay consumption % | -NCO∶-OH |
| PU-1 PU-2 PU-3 PU-4 PU-5 PU-6 PU-7 | 1 2 2 2 4 4 6 | 1.2∶1 1.2∶1 1.3∶1 1.4∶1 1.2∶1 1.3∶1 1.5∶1 |
The mass ratio of intercalation polyurethane solution and casein food grade sees Table 2 among the PUC.
Table 2 connects the material proportioning
| The PUC numbering | The PU type | The PU solid content | Casein food grade |
| PUC1 PUC2 PUC3 PUC4 PUC5 PUC6 PUC7 | PU1 PU2 PU1 PU5 PU3 PU6 PU7 | 5 5 10 5 5 5 15 | 20 20 15 20 20 20 10 |
The proportioning of table 3 water color ink
| Red black 1 | Yellow China ink 2 | ||
| PR185 (pigment) | 15 | PY86 (pigment) | 12 |
| PUC5 mould inhibitor ethanol water | 70 0.2 10 4.8 | PUC3 mould inhibitor ethanol water | 65 0.3 15 12.7 |
PR185, PY86 (being the international standard number of pigment)
The water color ink performance of table 4 preparation
| Stand linseed oil | Huang Mo | Red China ink | Lan Mo | |
| Viscosity (DIM, s) the fineness flash-point anti-vinylbenzene light fastness of ℃ anti-trimeric cyanamide (level) | 34 36 is good | 35 4 36 good 7 | 30 6 36 good 6 | 30 6 36 good 8 |
Claims (10)
1, a kind of preparation method of casein type aqueous ink comprises following processing step and processing condition:
(1) in solvent, add polyoxyethylene glycol or polyester diol, dimethylol propionic acid, isophorone diisocyanate, be warming up to 80～90 ℃, add the catalyzer di-n-butyltin dilaurate, carry out polyreaction, stop heating after 3～5 hours; Be cooled to 50～60 ℃, add the triethylamine neutralization, and adding entry, to be made into solid content be 20～40% polymers soln, adds the hydrophobic type clay in polymers soln that making clay weight concentration in solution is 1～6%, stirs to obtain clay intercalated urethane; Described reactive group isocyanate group and hydroxyl mol ratio are 1.1～1.5: 1, and described dimethylol propionic acid provides the hydroxyl mole number to account for 5～20% of total overall reaction thing hydroxyl mole number, and described dimethylol propionic acid mole number equates with the triethylamine mole number;
(2) under alkaline condition that casein food grade is water-soluble, preparation obtains the casein food grade aqueous solution of solid content 10～20%;
(3) with intercalation urethane and casein food grade aqueous solution evenly after, promptly obtain water color ink and connect material, connect in the material at water color ink and add pigment, ethanol, mould inhibitor and water, be ground to fineness 5～10 μ, transfer viscosity to 30～50 second, obtain water color ink; Described intercalation urethane accounts for and connects 5～20% of material weight percent.
2, the preparation method of casein type aqueous ink according to claim 1, it is characterized in that, water color ink connects material, pigment, ethanol, mould inhibitor and water by weight in the described step (3), water color ink connects 50～70 parts in material, 10～20 parts of pigment, 5～15 parts of ethanol, 0.1～0.5 part of mould inhibitor, 5～35 parts in water.
3, the preparation method of casein type aqueous ink according to claim 1 is characterized in that, solvent comprises acetone, pyrrolidone or vinyl acetic monomer in the described step (1).
4, the preparation method of casein type aqueous ink according to claim 1 is characterized in that, polyoxyethylene glycol is the polyoxyethylene glycol of molecular weight 400～600 in the described step (1).
5, the preparation method of casein type aqueous ink according to claim 1, it is characterized in that polyester diol is the poly-hexanodioic acid caprolactone dibasic alcohol of weight-average molecular weight 500～2000 or the own ester dibasic alcohol of hexanodioic acid of weight-average molecular weight 500～2000 in the described step (1).
6, the preparation method of casein type aqueous ink according to claim 1 is characterized in that, described step (2) neutral and alkali condition is a pH value 7.5～8.5.
7, the preparation method of casein type aqueous ink according to claim 1 is characterized in that, pigment is red, yellow, blue, black or veridian in the described step (3).
8, the preparation method of casein type aqueous ink according to claim 7 is characterized in that, described pigment photostabilization is 6～8 grades.
9, the preparation method of casein type aqueous ink according to claim 1 is characterized in that, mould inhibitor is an isothiazolinone in the described step (3).
10, a kind of casein type aqueous ink is exactly to be prepared from by each described preparation method of claim 1～8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100346999A CN100467550C (en) | 2006-03-31 | 2006-03-31 | Casein type aqueous ink and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100346999A CN100467550C (en) | 2006-03-31 | 2006-03-31 | Casein type aqueous ink and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827713A true CN1827713A (en) | 2006-09-06 |
| CN100467550C CN100467550C (en) | 2009-03-11 |
Family
ID=36946272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100346999A Expired - Fee Related CN100467550C (en) | 2006-03-31 | 2006-03-31 | Casein type aqueous ink and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100467550C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676340B (en) * | 2008-09-18 | 2011-08-17 | 浙江帝龙新材料股份有限公司 | Water-based ink specially used for decorative paper and manufacturing technique thereof |
| CN104151689A (en) * | 2014-07-24 | 2014-11-19 | 北京化工大学 | Preparation method of casein-containing halogen-free environment-friendly flame-retardant polymer |
| CN105368135A (en) * | 2015-12-08 | 2016-03-02 | 浙江帝龙新材料股份有限公司 | Anti-penetrating water-based ink used for decorative paper, and preparation method thereof |
| CN105705595A (en) * | 2013-11-11 | 2016-06-22 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed article |
| CN106085172A (en) * | 2016-06-02 | 2016-11-09 | 中国科学技术大学 | Bi-component waterborne colored paint based on water solublity dyeing firming agent and preparation method thereof |
| CN107384006A (en) * | 2017-05-05 | 2017-11-24 | 江苏唐彩油墨科技股份有限公司 | A kind of cork paper water-base gravure ink and preparation method thereof |
| CN107903709A (en) * | 2017-11-29 | 2018-04-13 | 苏州甫众塑胶有限公司 | A kind of preparation method of water-based ink binder |
| CN109233431A (en) * | 2018-07-24 | 2019-01-18 | 江苏唐彩油墨科技股份有限公司 | Water-borne decorative paper ink |
| CN111607288A (en) * | 2020-05-07 | 2020-09-01 | 杭州华大海天科技有限公司 | Casein type water-based pigment yellow ink-jet ink for titanium white paper and preparation method thereof |
-
2006
- 2006-03-31 CN CNB2006100346999A patent/CN100467550C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676340B (en) * | 2008-09-18 | 2011-08-17 | 浙江帝龙新材料股份有限公司 | Water-based ink specially used for decorative paper and manufacturing technique thereof |
| CN105705595A (en) * | 2013-11-11 | 2016-06-22 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed article |
| CN105705595B (en) * | 2013-11-11 | 2018-07-31 | 日立化成株式会社 | Adhesive for printing ink, flexible package laminating inks composition and printed article |
| CN104151689A (en) * | 2014-07-24 | 2014-11-19 | 北京化工大学 | Preparation method of casein-containing halogen-free environment-friendly flame-retardant polymer |
| CN105368135A (en) * | 2015-12-08 | 2016-03-02 | 浙江帝龙新材料股份有限公司 | Anti-penetrating water-based ink used for decorative paper, and preparation method thereof |
| CN105368135B (en) * | 2015-12-08 | 2018-12-11 | 浙江帝龙新材料有限公司 | Permeation-proof bottom water-based ink and its manufacturing process for facing paper |
| CN106085172A (en) * | 2016-06-02 | 2016-11-09 | 中国科学技术大学 | Bi-component waterborne colored paint based on water solublity dyeing firming agent and preparation method thereof |
| CN107384006A (en) * | 2017-05-05 | 2017-11-24 | 江苏唐彩油墨科技股份有限公司 | A kind of cork paper water-base gravure ink and preparation method thereof |
| CN107903709A (en) * | 2017-11-29 | 2018-04-13 | 苏州甫众塑胶有限公司 | A kind of preparation method of water-based ink binder |
| CN109233431A (en) * | 2018-07-24 | 2019-01-18 | 江苏唐彩油墨科技股份有限公司 | Water-borne decorative paper ink |
| CN109233431B (en) * | 2018-07-24 | 2021-04-13 | 江苏唐彩新材料科技股份有限公司 | Water-based decorative paper ink |
| CN111607288A (en) * | 2020-05-07 | 2020-09-01 | 杭州华大海天科技有限公司 | Casein type water-based pigment yellow ink-jet ink for titanium white paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100467550C (en) | 2009-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1827713A (en) | Casein type aqueous ink and method for preparing same | |
| CN101481451B (en) | High solid content latent curing polyurethane acroleic acid hybrid emulsion | |
| CN101544738B (en) | Room-temperature self-crosslinking water-soluble polyurethane acrylic resin and preparation method and application thereof | |
| JP6631964B1 (en) | Organic solvent-based printing ink having detachability, printed matter and laminate | |
| CN112694591A (en) | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane | |
| CN111333808A (en) | Preparation method of solvent-free waterborne polyurethane | |
| CN101033322A (en) | Room temperature crosslinking curing polyurethane-polyacrylic ester composite aqueous emulsion and preparing method thereof | |
| CN102093534A (en) | Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion | |
| CN106893065A (en) | A kind of fixation aqueous polyurethane dispersion, preparation method and applications | |
| CN113338051A (en) | Preparation method of solvent-free waterborne polyurethane microfiber synthetic leather with high R value | |
| CN105601567A (en) | Fluorochrome monomer, copolymeric fluorescent polyurethane emulsion and fluorescent polyurethane-acrylic ester copolymer emulsion as well as preparation methods thereof | |
| CN113637353A (en) | Ink binder and preparation method and application thereof | |
| CN1888001A (en) | Dry composite water-thined adhesive in soft package and its prepn | |
| CN111619257B (en) | Pyrograph film and production process thereof | |
| CN101157841A (en) | Preparation method of environment-friendly type aqueous polyurethane hot sol for clothing artificial leather | |
| CN104341572A (en) | Preparation method of solvent-free water-based polyurethane resin | |
| CN113121773A (en) | Sulfonic acid type solvent-free aqueous polyurethane resin and preparation method thereof | |
| CN111234602A (en) | High-adhesion color water-based ink for plastics and preparation method thereof | |
| CN112111191B (en) | PET (polyethylene terephthalate) heat transfer water-based ink without release agent and preparation method thereof | |
| CN112900107B (en) | Waterborne polyurethane/organic silicon composite mirror leather and preparation method thereof | |
| CN111269613B (en) | Gravure printing water-based ink and preparation method thereof | |
| CN114057980B (en) | Self-dispersible ester-soluble polyurethane ink resin, preparation method and ink | |
| CN110551418A (en) | water-based glitter gloss oil and preparation method thereof | |
| CN113527611B (en) | Polyurethane dispersion liquid and preparation method and application thereof | |
| CN115286955B (en) | EB (Electron beam) cured flame-retardant inkjet ink and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090311 Termination date: 20120331 |