CN112724739A - Tire code-spraying water-based ink composition and use method thereof - Google Patents
Tire code-spraying water-based ink composition and use method thereof Download PDFInfo
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- CN112724739A CN112724739A CN202011590295.4A CN202011590295A CN112724739A CN 112724739 A CN112724739 A CN 112724739A CN 202011590295 A CN202011590295 A CN 202011590295A CN 112724739 A CN112724739 A CN 112724739A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/58—Epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of ink, and particularly relates to a tire code-spraying water-based ink composition and a using method thereof. The water-based ink composition comprises the following raw material components, by weight, 70-100 parts of epoxy modified water-based polyurethane resin aqueous dispersion, 1-3 parts of water-based amino resin, 1-6 parts of pigment, 1-5 parts of adhesion promoter, 0.5-2 parts of dispersing agent, 0.5-0.8 part of anti-settling agent, 0.3-0.8 part of flatting agent and 0.6-1.2 parts of defoaming agent; the chain extender used in the preparation process of the epoxy modified aqueous polyurethane resin aqueous dispersion comprises a disulfide bond-containing diol selected from one or two of dithioethylene glycol and 1, 2-dithiopropylene glycol. The water-based ink composition disclosed by the invention is directly sprayed on a tire tread at the temperature of 70-100 ℃, and after the tire is vulcanized, the water-based ink composition is high in adhesive force, good in water resistance and good in temperature resistance, and is not easy to fade or discolor.
Description
Technical Field
The invention belongs to the technical field of ink, and relates to a tire code-spraying water-based ink composition and a using method thereof.
Background
The tire code-spraying ink is specially used for marking and spraying banburying tire tread rubber, is required to be resistant to vulcanization, has short drying time, does not change color after being vulcanized with a tire, is not stuck to a mold, is usually rolled on the tire tread by a marking device when the tire tread is extruded, is molded and vulcanized in a vulcanizing machine, and has important significance for improving the production efficiency of the tire.
The prior art discloses some tire inkjet inks, but the following problems exist: (1) the solvent-based ink has great pollution to the environment; (2) the adhesive force is not good after curing, and the adhesive is easy to fall off; (3) in the case of the water-based ink, the water resistance after curing is poor.
The water-based ink has the characteristic of environmental protection and is the development trend of the ink, but the water-based ink generally has the problems of poor adhesion on the surface of a substrate and poor water resistance after being cured. These problems are also present in tire inkjet inks.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the tire code-spraying water-based ink composition which has good adhesion to a tire after being cured, good water resistance and good temperature resistance and is not easy to discolor when the tire is vulcanized.
Another object of the present invention is to provide a method for using the tire spray ink composition.
The technical scheme of the invention is as follows:
a tire code-spraying water-based ink composition comprises, by weight, 70-100 parts of epoxy modified water-based polyurethane resin aqueous dispersion, 1-3 parts of water-based amino resin, 1-6 parts of pigment, 1-5 parts of adhesion promoter, 0.5-2 parts of dispersing agent, 0.5-0.8 part of anti-settling agent, 0.3-0.8 part of flatting agent and 0.6-1.2 parts of defoaming agent;
the chain extender used in the preparation process of the epoxy modified aqueous polyurethane resin aqueous dispersion comprises a disulfide bond-containing diol selected from one or two of dithioethylene glycol and 1, 2-dithiopropylene glycol.
In the invention, the pigment is water-based dye and can be selected from at least one of firm rose red, firm red lotus, pigment yellow 139, pigment red 254, hansha yellow 5GX and sun-proof yellow.
In the present invention, the dispersant may be one or more selected from the group consisting of an anionic dispersant, a cationic dispersant, a nonionic dispersant and an amphoteric dispersant. The anionic dispersant may be selected from sodium oleate, carboxylates, sulfate ester salts, sulfonates, and the like. The cationic dispersant may be selected from amine salts, quaternary ammonium salts, pyridinium salts, and the like. The nonionic dispersant is mainly polyethylene glycol polypropylene glycol type polyether, polyethylene glycol alkyl ether, acrylate polymer type dispersant, polyurethane or polyester polymer type dispersant. The amphoteric dispersant is mainly a phosphate type high molecular polymer.
In the invention, the anti-settling agent can be one or more selected from organic bentonite, castor oil derivatives, fumed silica, polyolefin wax, modified hydrogenated castor oil and polyamide wax.
In the present invention, the leveling agent may be selected from an organic silicon type leveling agent or an acrylate type leveling agent. The defoaming agent may be selected from organosilicon type defoaming agents.
According to a preferable technical scheme, the preparation method of the epoxy modified aqueous polyurethane resin aqueous dispersion comprises the steps of carrying out prepolymerization reaction on polyether diol, epoxy resin and diisocyanate at 70-100 ℃ for 2-4 hours, adding a chain extender mixture consisting of a small molecular chain extender, a hydrophilic chain extender and diol containing disulfide bonds, continuing to react for 4-10 hours, cooling to a temperature not higher than 50 ℃, adding acetone and triethylamine, stirring for 0.5-1 hour, adding water, emulsifying for 0.5-2 hours, and removing the acetone to obtain the epoxy modified aqueous polyurethane resin aqueous dispersion.
More preferably, the polyether diol is selected from polyethylene glycol, and the polymerization degree of the polyethylene glycol is 4-15.
As a more preferable technical scheme, the diisocyanate is selected from aliphatic diisocyanate or alicyclic diisocyanate, and can be selected from one or more of cyclohexane dimethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
More preferably, the molar ratio of the polyether glycol, the epoxy resin, the diisocyanate and the chain extender mixture is (0.2-0.5): 0.1-0.2): 1: (0.1-0.2).
As a more preferable technical scheme, the small molecule chain extender is selected from one or more of 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, neopentyl glycol and trimethylpentane glycol; the hydrophilic chain extender is one or two selected from dimethylolpropionic acid and dimethylolbutyric acid.
According to a more preferable technical scheme, the mole ratio of the micromolecule chain extender to the hydrophilic chain extender to the diol containing the disulfide bond in the chain extender mixture is 1 (0.7-2) to 0.05-0.3.
According to a further preferable technical scheme, the mole ratio of the micromolecule chain extender to the hydrophilic chain extender to the diol containing the disulfide bond in the chain extender mixture is 1 (0.7-2) to 0.1-0.22.
As a preferable technical scheme, the adhesion promoter is selected from silane coupling agents and can be selected from one of KBM-1003, KBM-403, KBM-503, KBE-903 and KBM-603 of Fungizone silicone (China) Limited.
A method for using the water-based ink composition of any one of the above embodiments, the water-based ink composition is directly sprayed on a tire tread at 70-100 ℃, and the tire is heated and vulcanized. Generally, the temperature at which the tire is heated and vulcanized is about 150 ℃.
The invention has the beneficial effects that:
(1) in the invention, chain extension is carried out on the epoxy modified aqueous polyurethane resin aqueous dispersion through diol containing disulfide bonds, and disulfide bonds are introduced into the molecular structure of the epoxy modified polyurethane. When the water-based ink is applied to the tire tread, the tire is heated and vulcanized, under the action of a vulcanizing agent, disulfide bonds in the molecular structure of the epoxy modified polyurethane are broken and participate in the vulcanization reaction of the tire tread rubber, and the epoxy modified polyurethane molecules and the tire tread rubber are chemically combined, so that the water-based ink has good adhesive force on the tire tread.
(2) According to the invention, by controlling the addition amount of the diol containing the disulfide bond, the molecular weight of the epoxy modified polyurethane is not low after the disulfide bond is broken, so that the ink has better wear resistance after being cured.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts described in the following examples are parts by weight.
Examples 1 to 4 preparation of epoxy-modified aqueous polyurethane resin Dispersion
Example 1
Selecting raw materials, wherein polyether diol is selected from polyethylene glycol (the polymerization degree is 10), and diisocyanate is selected from cyclohexane dimethylene diisocyanate; the micromolecular chain extender is 1, 2-propylene glycol; the hydrophilic chain extender is dimethylolpropionic acid; the disulfide bond-containing dihydric alcohol is dithioglycol; the molar ratio of the polyethylene glycol to the epoxy resin E51 to the chain extender mixture is 0.22:0.15:1: 0.12; the mol ratio of the 1, 2-propylene glycol, the dimethylolpropionic acid and the dithioglycol is 1:0.8:0.1,
carrying out prepolymerization reaction on polyethylene glycol, epoxy resin E51 and cyclohexane dimethylene diisocyanate at 75-80 ℃ for 2.5 hours, adding a chain extender mixture consisting of 1, 2-propylene glycol, dimethylolpropionic acid and dithioglycol, continuing to react for 7 hours, cooling to 45 ℃, adding a proper amount of acetone and triethylamine, stirring for 0.5 hour, adding deionized water under vigorous stirring for emulsification for 0.7 hour, removing the acetone to obtain the epoxy modified aqueous polyurethane resin aqueous dispersion with the weight concentration of 35%, and marking as W-1.
Example 2
Selecting raw materials, wherein polyether diol is selected from polyethylene glycol (the polymerization degree is 6.2), and diisocyanate is selected from isophorone diisocyanate; the micromolecular chain extender is 1, 3-propylene glycol; the hydrophilic chain extender is dimethylolbutyric acid; the disulfide bond-containing dihydric alcohol is 1, 2-dithio propylene glycol; the molar ratio of the polyethylene glycol to the epoxy resin E44 to the chain extender mixture is 0.35:0.12:1: 0.17; the mol ratio of the 1, 3-propanediol to the dimethylolbutyric acid to the 1, 2-dithio-propanediol is 1:1.6:0.18,
carrying out prepolymerization reaction on polyethylene glycol, epoxy resin E44 and isophorone diisocyanate at 80-85 ℃ for 3 hours, adding a chain extender mixture consisting of 1, 3-propylene glycol, dimethylolbutyric acid and 1, 2-dithiopropylene glycol, continuing to react for 8 hours, cooling to 45 ℃, adding a proper amount of acetone and triethylamine, stirring for 0.6 hour, adding deionized water under vigorous stirring for emulsification for 0.7 hour, removing the acetone, and obtaining the epoxy modified waterborne polyurethane resin aqueous dispersion with the weight concentration of 40%, which is recorded as W-2.
Example 3
Selecting raw materials, wherein polyether diol is selected from polyethylene glycol (the polymerization degree is 12.9), and diisocyanate is selected from hexamethylene diisocyanate; the micromolecular chain extender is neopentyl glycol; the hydrophilic chain extender is dimethylolbutyric acid; the disulfide bond-containing dihydric alcohol is dithioglycol; the molar ratio of the polyethylene glycol to the epoxy resin E51 to the chain extender mixture is 0.44:0.18:1: 0.2; the mol ratio of neopentyl glycol, dimethylol butyric acid and dithioglycol is 1:1.4:0.21,
carrying out prepolymerization reaction on polyethylene glycol, epoxy resin E51 and hexamethylene diisocyanate at 90-95 ℃ for 4 hours, adding a chain extender mixture consisting of neopentyl glycol, dimethylolbutyric acid and dithioglycol, continuing to react for 6.5 hours, cooling to 40 ℃, adding a proper amount of acetone and triethylamine, stirring for 1 hour, adding deionized water under vigorous stirring for emulsification for 1 hour, and removing acetone to obtain the epoxy modified waterborne polyurethane resin aqueous dispersion with the weight concentration of 31%, wherein the weight concentration is marked as W-3.
Example 4
Selecting raw materials, wherein polyether diol is selected from polyethylene glycol (the polymerization degree is 10), and diisocyanate is selected from dicyclohexylmethane diisocyanate; the micromolecular chain extender is 2-methyl-1, 3-propylene glycol; the hydrophilic chain extender is dimethylolpropionic acid; the disulfide bond-containing dihydric alcohol is 1, 2-dithio propylene glycol; the molar ratio of the polyethylene glycol to the epoxy resin E44 to the chain extender mixture is 0.5:0.15:1: 0.16; the mol ratio of the 2-methyl-1, 3-propanediol, the dimethylolpropionic acid and the 1, 2-dithio-propanediol is 1:2:0.27,
carrying out prepolymerization reaction on polyethylene glycol, epoxy resin E44 and dicyclohexylmethane diisocyanate at 90-95 ℃ for 2.5 hours, adding a chain extender mixture consisting of 2-methyl-1, 3-propanediol, dimethylolpropionic acid and 1, 2-dithio-propanediol, continuing to react for 8 hours, cooling to 40 ℃, adding an appropriate amount of acetone and triethylamine, stirring for 0.6 hour, adding deionized water under vigorous stirring for emulsification for 1.2 hours, removing acetone, and obtaining the epoxy modified waterborne polyurethane resin aqueous dispersion with the weight concentration of 38%, which is recorded as W-4.
Examples 5 to 12 preparation of aqueous ink compositions
Example 5
70 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-1, 1 part of aqueous amino resin, 3 parts of firm rose bengal, 1.2 parts of KBM-1003, 0.7 part of polyacrylate super-dispersant, 0.6 part of organic bentonite, 0.4 part of polyether organic silicon flatting agent and 0.7 part of organic silicon defoaming agent dispersed with white carbon black,
adding aqueous amino resin, firm rose bengal and polyacrylate super dispersant into an epoxy modified aqueous polyurethane resin aqueous dispersion W-1, violently stirring and dispersing, adding organic bentonite and a polyether organic silicon leveling agent, stirring and dispersing, adding an organic silicon defoamer dispersed with white carbon black, violently stirring and dispersing, passing through a one-time three-roll machine, adding a silane coupling agent KBM-1003, stirring and dispersing, and filtering to obtain an aqueous ink composition 1.
Example 6
80 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-1, 2 parts of aqueous amino resin, 2 parts of pigment yellow 139, 1.5 parts of KBM-503, 1.2 parts of polyurethane macromolecular dispersant, 0.5 part of fumed silica, 0.5 part of polyether organic silicon flatting agent and 0.9 part of organic silicon defoaming agent dispersed with white carbon black,
adding aqueous amino resin, pigment yellow 139 and polyurethane macromolecular dispersant into the epoxy modified aqueous polyurethane resin aqueous dispersion W-1, violently stirring and dispersing, adding fumed silica and polyether organic silicon leveling agent, stirring and dispersing, adding the organic silicon defoamer dispersed with white carbon black, violently stirring and dispersing, passing through a one-time three-roll machine, adding the silane coupling agent KBM-503, stirring and dispersing, and filtering to obtain the aqueous ink composition 2.
Example 7
90 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-2, 2 parts of aqueous amino resin, 4 parts of pigment red 254, 2 parts of KBM-403, 0.9 part of polyacrylate super-dispersant, 0.8 part of organic bentonite, 0.5 part of acrylate type flatting agent and 0.9 part of organic silicon defoaming agent,
adding aqueous amino resin, pigment red 254 and polyacrylate super-dispersant into the epoxy modified aqueous polyurethane resin aqueous dispersion W-2, violently stirring and dispersing, adding organic bentonite and an acrylate leveling agent, stirring and dispersing, adding an organic silicon defoaming agent, violently stirring and dispersing, passing through a one-time three-roll machine, adding a silane coupling agent KBM-403, stirring and dispersing, and filtering to obtain the aqueous ink composition 3.
Example 8
100 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-2, 3 parts of aqueous amino resin, 4 parts of lightfast yellow, 3 parts of KBM-503, 1.5 parts of polyester type macromolecular dispersant, 0.8 part of modified hydrogenated castor oil, 0.6 part of acrylate type flatting agent and 1.2 parts of organic silicon defoaming agent,
adding aqueous amino resin, fast yellow and polyester type high molecular dispersing agent into the epoxy modified aqueous polyurethane resin aqueous dispersion W-2, violently stirring and dispersing, adding modified hydrogenated castor oil and acrylate type leveling agent, stirring and dispersing, adding organic silicon defoamer, violently stirring and dispersing, passing through a one-time three-roll machine, adding silane coupling agent KBM-503, stirring and dispersing, and filtering to obtain the aqueous ink composition 4.
Example 9
75 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-3, 2 parts of aqueous amino resin, 3.5 parts of firm rose bengal, 1.5 parts of KBE-903, 1 part of acrylate hyper-dispersant, 0.7 part of fumed silica, 0.5 part of polyether organic silicon flatting agent and 1.0 part of organic silicon defoaming agent,
adding aqueous amino resin, firm rose bengal and acrylate hyper-dispersant into the epoxy modified aqueous polyurethane resin aqueous dispersion W-3, violently stirring and dispersing, then adding fumed silica and polyether organic silicon leveling agent, stirring and dispersing, adding organic silicon defoamer, violently stirring and dispersing, passing through a one-time three-roll machine, then adding silane coupling agent KBE-903, stirring and dispersing, and filtering to obtain the aqueous ink composition 5.
Example 10
85 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-3, 1 part of aqueous amino resin, 2.5 parts of Hansa yellow 5GX, 1.3 parts of KBM-603, 1.7 parts of polyethylene glycol alkyl ether dispersant, 0.5 part of organic bentonite, 0.6 part of polyether organic silicon flatting agent and 1.0 part of organic silicon defoaming agent,
adding aqueous amino resin, Hansa yellow 5GX and polyethylene glycol alkyl ether dispersing agent into the epoxy modified aqueous polyurethane resin aqueous dispersion W-3, violently stirring and dispersing, then adding organic bentonite and polyether organic silicon flatting agent, stirring and dispersing, adding organic silicon defoaming agent, violently stirring and dispersing, passing through a one-time three-roll machine, then adding silane coupling agent KBM-603, stirring and dispersing, and filtering to obtain aqueous ink composition 6.
Example 11
95 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-4, 3 parts of aqueous amino resin, 2 parts of firm red lotus, 1.7 parts of KBM-503, 1.2 parts of acrylate hyper-dispersant, 0.6 part of organic bentonite, 0.6 part of polyether organic silicon flatting agent and 1.0 part of organic silicon defoaming agent,
adding aqueous amino resin, firm red lotus and acrylate hyper-dispersant into the epoxy modified aqueous polyurethane resin aqueous dispersion W-4, violently stirring and dispersing, then adding organic bentonite and polyether organic silicon flatting agent, stirring and dispersing, adding organic silicon defoamer, violently stirring and dispersing, passing through a one-time three-roll machine, then adding silane coupling agent KBM-503, stirring and dispersing, and filtering to obtain the aqueous ink composition 7.
Example 12
100 parts of epoxy modified aqueous polyurethane resin aqueous dispersion W-4, 1 part of aqueous amino resin, 3 parts of pigment yellow 139, 1.5 parts of KBE-903, 1 part of acrylate hyper-dispersant, 0.8 part of modified hydrogenated castor oil, 0.6 part of polyether organic silicon flatting agent and 1.0 part of organic silicon defoaming agent,
adding aqueous amino resin, pigment yellow 139 and acrylate hyper-dispersant into the epoxy modified aqueous polyurethane resin aqueous dispersion W-4, violently stirring and dispersing, adding modified hydrogenated castor oil and polyether organic silicon flatting agent, stirring and dispersing, adding organic silicon defoamer, violently stirring and dispersing, passing through a one-time three-roll machine, adding silane coupling agent KBE-903, stirring and dispersing, and filtering to obtain the aqueous ink composition 8.
Comparative example 1
In example 2, the molar ratio of 1, 3-propanediol, dimethylolbutyric acid and 1, 2-dithiopropanediol was 1:1.6:0.35, and the remaining steps were kept unchanged to obtain an aqueous epoxy-modified aqueous polyurethane resin dispersion, denoted as W-5.
In example 7, the epoxy-modified aqueous polyurethane resin aqueous dispersion W-2 was replaced with the epoxy-modified aqueous polyurethane resin aqueous dispersion W-5, and the remainder was kept unchanged to obtain an aqueous ink composition 9.
Comparative example 2
In example 2, the molar ratio of 1, 3-propanediol, dimethylolbutyric acid and 1, 2-dithiopropanediol was 1:1.6:0.03, and the remaining steps were kept unchanged to obtain an aqueous epoxy-modified aqueous polyurethane resin dispersion, denoted as W-6.
In example 7, the epoxy-modified aqueous polyurethane resin aqueous dispersion W-2 was replaced with the epoxy-modified aqueous polyurethane resin aqueous dispersion W-6, and the remainder was kept unchanged to obtain an aqueous ink composition 10.
Comparative example 3
In example 2, 1, 2-dithiopropylene glycol was not added, the molar ratio of 1, 3-propylene glycol to dimethylolbutyric acid was 1:1.8, and the remaining steps were kept unchanged to obtain an epoxy-modified aqueous polyurethane resin aqueous dispersion, which was designated as W-7.
In example 7, the epoxy-modified aqueous polyurethane resin aqueous dispersion W-2 was replaced with the epoxy-modified aqueous polyurethane resin aqueous dispersion W-7, and the remainder was kept unchanged to obtain an aqueous ink composition 11.
Results testing
The water-based ink compositions 1-11 obtained in the above embodiments are directly sprayed on a tire tread at 90 ℃, and then the tire tread is completely vulcanized in an environment of 150 ℃.
Cold water resistance test: taking out the vulcanized tire, immediately soaking the vulcanized tire into ice water at 0 ℃ for 30 minutes, taking out the tire, wiping the tire dry, and observing whether the ink drops. The results are shown in Table 1.
Testing for water immersion resistance; and (3) placing the vulcanized tire at room temperature for 24 hours, soaking the vulcanized tire in deionized water at 50 ℃ for 500 hours, taking out the vulcanized tire, wiping the vulcanized tire dry, and observing whether the printing ink has a shedding phenomenon. The results are shown in Table 1.
And (3) testing the adhesive force: the test was carried out according to the method GB/T9286-1998 test for the test of the paint film of the paints and varnishes. The ink adhesion is classified into 0, 1,2, 3, 4 and 5 grades, with 0 grade being the best and 5 grade being the worst. The results are shown in Table 1.
And (3) high temperature resistance test: the tire tread was baked at 150 ℃ for 2 hours and the ink was observed for discoloration, fading or falling off. The results are shown in Table 1.
And (3) wear resistance test: and (3) adopting a rotary friction and wear measuring instrument to test whether the printing ink falls off or not at the rotating speed of 500rpm for 5 minutes. The results are shown in Table 1.
TABLE 1
Remarking: o represents that the test is passed and no adverse change occurs; x indicates that the test failed and an undesirable change occurred.
The results in table 1 show that, in the preparation method of the epoxy-modified aqueous polyurethane resin aqueous dispersion, the disulfide bond-containing diol is added, and the obtained epoxy-modified aqueous polyurethane resin aqueous dispersion is applied to tire code-spraying aqueous ink, and the performance is better than that of the epoxy-modified aqueous polyurethane resin aqueous dispersion without the disulfide bond-containing diol. By controlling the content of the disulfide bond dihydric alcohol in the chain extender mixture, the tire code-spraying water-based ink composition with excellent adhesive force, cold water resistance, water immersion resistance, wear resistance and high temperature resistance is obtained.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A tire code-spraying water-based ink composition is characterized by comprising the following raw material components, by weight, 70-100 parts of epoxy modified water-based polyurethane resin aqueous dispersion, 1-3 parts of water-based amino resin, 1-6 parts of pigment, 1-5 parts of adhesion promoter, 0.5-2 parts of dispersing agent, 0.5-0.8 part of anti-settling agent, 0.3-0.8 part of leveling agent and 0.6-1.2 parts of defoaming agent;
the chain extender used in the preparation process of the epoxy modified aqueous polyurethane resin aqueous dispersion comprises a disulfide bond-containing diol selected from one or two of dithioethylene glycol and 1, 2-dithiopropylene glycol.
2. The aqueous ink composition according to claim 1, wherein the preparation method of the epoxy-modified aqueous polyurethane resin aqueous dispersion comprises the steps of carrying out prepolymerization reaction on polyether diol, epoxy resin and diisocyanate at 70-100 ℃ for 2-4 hours, adding a chain extender mixture consisting of a small-molecule chain extender, a hydrophilic chain extender and disulfide bond-containing diol, continuing the reaction for 4-10 hours, cooling to a temperature not higher than 50 ℃, adding acetone and triethylamine, stirring for 0.5-1 hour, adding water, emulsifying for 0.5-2 hours, and removing the acetone to obtain the epoxy-modified aqueous polyurethane resin aqueous dispersion.
3. The aqueous ink composition according to claim 2, wherein the polyether glycol is selected from polyethylene glycol, and the polymerization degree of the polyethylene glycol is 4 to 15.
4. The aqueous ink composition according to claim 2, the diisocyanate being selected from an aliphatic diisocyanate or a cycloaliphatic diisocyanate.
5. The aqueous ink composition according to claim 2, wherein the molar ratio of the polyether glycol, the epoxy resin, the diisocyanate and the chain extender mixture is (0.2-0.5): 0.1-0.2): 1: (0.1-0.2).
6. The aqueous ink composition according to claim 2, wherein the small molecule chain extender is selected from one or more of 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, neopentyl glycol and trimethylpentane glycol; the hydrophilic chain extender is one or two selected from dimethylolpropionic acid and dimethylolbutyric acid.
7. The aqueous ink composition according to claim 2, wherein the molar ratio of the small molecular chain extender to the hydrophilic chain extender to the disulfide bond-containing diol in the chain extender mixture is 1 (0.7-2) to (0.05-0.3).
8. The aqueous ink composition according to claim 7, wherein the molar ratio of the small molecular chain extender to the hydrophilic chain extender to the disulfide bond-containing diol in the chain extender mixture is 1 (0.7-2) to (0.1-0.22).
9. The aqueous ink composition according to claim 1, the adhesion promoter being selected from silane coupling agents.
10. A method of using the aqueous ink composition according to any one of claims 1 to 9, wherein the aqueous ink composition is directly sprayed on a tire tread at 70 to 100 ℃, and the tire is heat-vulcanized.
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| CN114106606A (en) * | 2021-12-16 | 2022-03-01 | 青岛大学 | Tire discoloration prevention protective liquid and preparation method thereof |
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| CN105778039A (en) * | 2016-05-20 | 2016-07-20 | 武汉科技大学 | Aqueous polyurethane dispersion subjected to post-chain extension through click chemistry and preparation method thereof |
| CN108084785A (en) * | 2017-12-18 | 2018-05-29 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and water-based ink resin |
| CN108948863A (en) * | 2018-08-17 | 2018-12-07 | 厦门格林泰新材料科技有限公司 | A kind of aqueous coding ink and preparation method thereof on rubber tyre |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105778039A (en) * | 2016-05-20 | 2016-07-20 | 武汉科技大学 | Aqueous polyurethane dispersion subjected to post-chain extension through click chemistry and preparation method thereof |
| CN108084785A (en) * | 2017-12-18 | 2018-05-29 | 广州聚碳合成材料有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and water-based ink resin |
| CN108948863A (en) * | 2018-08-17 | 2018-12-07 | 厦门格林泰新材料科技有限公司 | A kind of aqueous coding ink and preparation method thereof on rubber tyre |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114106606A (en) * | 2021-12-16 | 2022-03-01 | 青岛大学 | Tire discoloration prevention protective liquid and preparation method thereof |
| CN114106606B (en) * | 2021-12-16 | 2022-11-29 | 青岛大学 | Tire discoloration prevention protective liquid and preparation method thereof |
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