CN108840992B - Water-based ink composition, water-based ink resin, and preparation method and application thereof - Google Patents
Water-based ink composition, water-based ink resin, and preparation method and application thereof Download PDFInfo
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- CN108840992B CN108840992B CN201810469093.0A CN201810469093A CN108840992B CN 108840992 B CN108840992 B CN 108840992B CN 201810469093 A CN201810469093 A CN 201810469093A CN 108840992 B CN108840992 B CN 108840992B
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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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
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- 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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- 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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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Abstract
The invention relates to the field of water-based ink, and discloses a water-based ink composition, a water-based ink resin, and a preparation method and application thereof. An aqueous ink composition. Wherein, the composition comprises the following components in percentage by weight: (1) 20-35 wt% of a hydroxyl-terminated polyamide-ether resin; (2) 5-15 wt% of diisocyanate; (3) 2-10 wt% of a glycol; (4) 2-10 wt% of diamine sulfonate; (5) 1-6 wt% of epoxy alcohol; (6) 45-65 wt% of water. The water-based ink resin prepared from the water-based ink composition has good adhesion fastness and good printability. After the water-based ink prepared from the water-based ink resin is printed on a packaging base material, the water-based ink has the advantages of water boiling resistance and boiling resistance.
Description
Technical Field
The invention relates to the field of water-based ink, in particular to a water-based ink composition, water-based ink resin, a preparation method and application thereof.
Background
The high-temperature-resistant steamed and boiled food has long shelf life, can be eaten cold or hot, and is convenient to carry, thus being popular with consumers. After the food is packaged, the food is generally subjected to a high-temperature water boiling or steaming process, so that higher requirements are put on the packaging of the food. The packaging base material is required to withstand high temperature test, and the printed and compounded packaging bag is required to have higher composite strength. With the enhancement of domestic environmental protection consciousness, the ink products for soft packaging in China are rapidly developing towards the environmental protection and sanitation directions. The water-based ink has the advantages of no toxicity, no pungent smell, no corrosiveness, no combustion, no explosion, good use safety and no harm to the environment and human bodies, and belongs to a typical green environment-friendly product.
CN104059429B discloses a water-soluble inner printing composite plastic ink which adopts water-soluble acrylic acid modified resin as an ink binder. The water-soluble resin has poor adhesive force to base materials, so that the water-soluble resin cannot meet the requirements of water boiling resistance and cooking resistance.
The waterborne polyurethane is an environment-friendly material taking water as a dispersion medium, and is widely applied to the fields of adhesives, coatings, leatherworking, textile auxiliaries, medicine and health, building materials, printing and the like. Development of aqueous inks using aqueous polyurethanes as ink vehicles has attracted extensive attention from research and development personnel. US5470907 discloses a preparation method of aqueous polyurethane emulsion using dimethylolpropionic acid as hydrophilic chain extender, but due to the catalytic hydrolysis of carboxyl, the prepared polyurethane emulsion has poor hydrolysis resistance after film formation. Therefore, the waterborne polyurethane in the general sense is difficult to meet the requirements of steam-resistant packaging under the actions of high temperature, high humidity and water vapor penetration damage.
In recent years, ink for general light packaging has been increasing in the market. However, the effect of the water-based ink for retort-resistant packaging is difficult to satisfy at present, so that the development of the water-based ink for retort resistance and retort resistance is one step which is inevitably taken out for the environmental protection of the ink.
Disclosure of Invention
The invention aims to solve the problem that the water-based ink for packaging in the prior art cannot meet the requirements of water boiling resistance and boiling resistance, and provides a water-based ink composition, a water-based ink resin, a preparation method and an application thereof. After the water-based ink prepared from the water-based ink resin is printed on a packaging base material, the water-based ink has the advantages of water boiling resistance and boiling resistance.
In order to achieve the above object, a first aspect of the present invention provides an aqueous ink composition, wherein the composition comprises the following components in percentage by weight:
preferably, the hydroxyl value of the hydroxyl-terminated polyamide-ether resin is 28-56 mg (KOH)/g.
Preferably, the hydroxyl-terminated polyamide-ether resin is at least one of a hydroxyl-terminated polyamide-polyoxyethylene glycol resin, a hydroxyl-terminated polyamide-polyoxypropylene glycol resin, a hydroxyl-terminated polyamide-polytetrahydrofuran glycol resin, a hydroxyl-terminated polyamide-oxypropylene-oxyethylene copolyol resin, a hydroxyl-terminated polyamide-tetrahydrofuran-oxypropylene copolyol resin, and a hydroxyl-terminated polyamide-tetrahydrofuran-oxyethylene copolyol resin.
Preferably, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dimethylene benzene diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the diol is at least one of 2, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, neopentyl glycol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, hydrogenated bisphenol a, 2-isopropyl-1, 4-butanediol, 3-methyl-1, 5-pentanediol, 2, 4-dimethyl-1, 5-pentanediol.
Preferably, the diamine sulfonate is at least one of 2- (2-amino-cyclohexylamino) -ethanesulfonic acid sodium salt, 2- [ (5-amino-1, 3, 3-trimethyl-cyclohexylmethyl) -amino ] -ethanesulfonic acid sodium salt, 2- [4- (4-amino-cyclohexylmethyl) -cyclohexylamino ] -ethanesulfonic acid sodium salt, N- (2-aminoethyl) -aminoethanesulfonic acid sodium salt, ethylenediamine ethanesulfonic acid sodium salt, 2, 4-diaminobenzene sulfonic acid sodium salt and 2, 6-diaminobenzene sulfonic acid sodium salt.
Preferably, the epoxy alcohol is propylene oxide and/or butylene oxide.
The second aspect of the present invention provides a method for preparing an aqueous ink resin from the above aqueous ink composition, wherein the method comprises the steps of:
(1) carrying out a first reaction on hydroxyl-terminated polyamide-ether resin and diisocyanate, adding dihydric alcohol for a second reaction, cooling to room temperature, adding acetone, then adding diamine sulfonate for a third reaction, and adding epoxy alcohol for a fourth reaction to obtain a polymer;
(2) and (3) contacting the polymer with water to disperse, and removing acetone to obtain the water-based ink resin.
According to an embodiment of the present invention, the method for preparing the aqueous ink resin from the aqueous ink composition described above may be:
(1) adding hydroxyl-terminated polyamide-ether resin and diisocyanate into a reaction kettle I, heating to 80-100 ℃, reacting for 1-2 hours, adding dihydric alcohol, reacting for 1-2 hours, cooling to room temperature, adding a proper amount of acetone to reduce the viscosity of reactants, adding diamine sulfonate, stirring at room temperature for reacting for 0.5-1 hour, heating to 60-70 ℃, adding epoxy alcohol, and reacting for 1-2 hours to obtain the polymer.
(2) And adding water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.5-1 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
In a third aspect, the present invention provides an aqueous ink resin prepared by the above method.
The fourth aspect of the invention provides the application of the water-based ink resin in printing ink, coating and adhesive.
The invention adopts the hydroxyl-terminated polyamide-ether resin as the soft segment, improves the adhesion fastness of the water-based ink resin and the packaging base material, and avoids the problem of polymer degradation caused by poor hydrolysis resistance of ester bonds when common polyester is adopted. Secondly, the invention adopts diamine sulfonate as a chain extender, so that the molecular weight of the waterborne polyurethane is not reduced, and simultaneously, the content of hydrophilic groups in the polymer is reduced, thereby improving the water resistance of the waterborne ink resin. Moreover, the epoxy group (epoxy alcohol) is introduced, so that the subsequent crosslinking and curing of the water-based ink resin can be performed, and the adhesive force of the water-based ink resin is greatly improved. The combination of the above points reduces the destructive effect of water vapor on the water-based ink resin under high temperature and high humidity conditions, and improves the boiling resistance and steaming resistance of the prepared water-based ink.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a water-based ink composition, wherein the composition comprises the following components in percentage by weight:
in the invention, the hydroxyl value of the hydroxyl-terminated polyamide-ether resin can be 28-56 mg (KOH)/g, and the hydroxyl-terminated polyamide-ether resin under the hydroxyl value is more favorable for improving the adhesion fastness of the water-based ink resin to a substrate.
In the present invention, the hydroxyl-terminated polyamide-ether resin is capable of acting as a soft segment and having hydrolysis resistance, and may be, for example, but not limited to: at least one of a hydroxyl-terminated polyamide-polyoxyethylene glycol resin, a hydroxyl-terminated polyamide-polyoxypropylene glycol resin, a hydroxyl-terminated polyamide-polytetrahydrofuran glycol resin, a hydroxyl-terminated polyamide-oxypropylene-oxyethylene copolyol resin, a hydroxyl-terminated polyamide-tetrahydrofuran-oxypropylene copolyol resin, and a hydroxyl-terminated polyamide-tetrahydrofuran-oxyethylene copolyol resin.
In the present invention, the diisocyanate may be, but is not limited to: at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
In the present invention, the diol as a chain extender may be, but is not limited to: 2, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, neopentyl glycol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 2-isopropyl-1, 4-butanediol, 3-methyl-1, 5-pentanediol, 2, 4-dimethyl-1, 5-pentanediol.
In the present invention, the diamine sulfonate is used as a chain extender, and for the purpose of increasing the molecular weight of the aqueous polyurethane and reducing the content of the hydrophilic group in the polymer, for example, but not limited to: 2- (2-amino-cyclohexylamino) -ethanesulfonic acid sodium salt, 2- [ (5-amino-1, 3, 3-trimethyl-cyclohexylmethyl) -amino ] -ethanesulfonic acid sodium salt, 2- [4- (4-amino-cyclohexylmethyl) -cyclohexylamino ] -ethanesulfonic acid sodium salt, N- (2-aminoethyl) -aminoethanesulfonic acid sodium salt, ethylenediamine ethanesulfonic acid sodium salt, 2, 4-diaminobenzenesulfonic acid sodium salt, 2, 6-diaminobenzenesulfonic acid sodium salt.
In the present invention, the epoxy alcohol is used for promoting the post-crosslinking curing, and may be, for example, but not limited to: propylene oxide and/or butylene oxide.
The second aspect of the present invention provides a method for preparing an aqueous ink resin from the above aqueous ink composition, wherein the method comprises the steps of:
(1) carrying out a first reaction on hydroxyl-terminated polyamide-ether resin and diisocyanate, adding dihydric alcohol for a second reaction, cooling to room temperature, adding acetone, then adding diamine sulfonate for a third reaction, and adding epoxy alcohol for a fourth reaction to obtain a polymer;
(2) and (3) contacting the polymer with water to disperse, and removing acetone to obtain the water-based ink resin.
According to the process of the present invention, the conditions of the first reaction include, but are not limited to: the temperature is 80-100 ℃, and the time is 1-2 h.
According to the process of the present invention, the conditions of the second reaction include, but are not limited to: the temperature is 80-100 ℃, and the time is 1-2 h.
According to the process of the present invention, the conditions of the third reaction include, but are not limited to: the temperature is room temperature, and the time is 0.5-1 h.
According to the process of the present invention, the conditions of the fourth reaction include, but are not limited to: the temperature is 60-70 ℃, and the time is 1-2 h.
According to the method of the present invention, the conditions of the dispersion may include, but are not limited to: the temperature is room temperature, and the time is 0.5-1 h.
According to the method of the present invention, the acetone is added in an amount determined by the viscosity of the reactant so that the viscosity of the reactant can be reduced and the reactant can be uniformly stirred, and if the viscosity is too high, the amount of acetone can be increased in an appropriate amount, and if the viscosity is low, the amount of acetone can be decreased in an appropriate amount, and since the step of removing acetone is performed in step (2), the amount of acetone can be added as needed.
In a third aspect, the present invention provides an aqueous ink resin prepared by the above method.
The water-based ink resin has good adhesion and good printability, is environment-friendly, and can meet the packaging requirements of water boiling and steaming at different levels.
The fourth aspect of the invention provides the application of the water-based ink resin in printing ink, coating and adhesive.
The ink prepared from the water-based ink resin can meet the requirements of water boiling resistance and steaming resistance after being used for a packaging substrate.
The application of the above aqueous ink is not limited thereto.
The present invention will be described in detail below by way of examples.
Example 1
(1) 15kg of hydroxyl-terminated polyamide-polyoxyethylene glycol resin (hydroxyl value: 32mg (KOH))/g), 6kg of hydroxyl-terminated polyamide-tetrahydrofuran-propylene oxide copolymerized glycol resin (hydroxyl value: 36mg (KOH))/g) and 13kg of toluene diisocyanate were added to a reaction vessel I, heated to 80 ℃ to react for 2 hours, 7kg of 2, 2-dimethyl-1, 3-propanediol was added to react for 1.2 hours, an appropriate amount of acetone was added to reduce the viscosity of the reaction product after cooling to room temperature, 10kg of 2- (2-amino-cyclohexylamino) -sodium ethanesulfonate was added to the reaction vessel I, stirred at room temperature to react for 0.6 hours, heated to 60 ℃ and 4kg of epoxypropanol was added to react for 1.8 hours, thus obtaining a polymer.
(2) And adding 45kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.5 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Example 2
(1) 27.5kg of hydroxyl-terminated polyamide-polyoxypropylene glycol resin (hydroxyl value: 40mg (KOH)/g), 4kg of diphenylmethane diisocyanate and 6kg of dicyclohexylmethane diisocyanate were added to a reaction vessel I, heated to 90 ℃ and reacted for 1.4 hours, 2kg of 2-ethyl-2-butyl-1, 3-propanediol was added and reacted for 1 hour, an appropriate amount of acetone was added to reduce the viscosity of the reaction product after cooling to room temperature, 7kg of sodium 2- [ (5-amino-1, 3, 3-trimethyl-cyclohexylmethyl) -amino ] -ethanesulfonate was added, the reaction was stirred at room temperature for 0.75 hour, heated to 65 ℃ and reacted for 1.4 hours with 3.5kg of epoxy butanol to obtain a polymer.
(2) And adding 50kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.6 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Example 3
(1) Adding 35kg of hydroxyl-terminated polyamide-polytetrahydrofuran diol resin (hydroxyl value is 28mg (KOH)/g) and 5.5kg of hexamethylene diisocyanate into a reaction kettle I, heating to 100 ℃, reacting for 1.8 hours, adding 2kg of neopentyl glycol and 4kg of 2, 4-dimethyl-1, 5-pentanediol, reacting for 1.4 hours, cooling to room temperature, adding a proper amount of acetone to reduce the viscosity of a reactant, adding 2kg of 2- [4- (4-amino-cyclohexylmethyl) -cyclohexylamino ] -ethanesulfonic acid sodium, stirring at room temperature for reacting for 1 hour, heating to 70 ℃, adding 6kg of epoxy propanol, and reacting for 2 hours to obtain the polymer.
(2) And adding 45.5kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.75 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Example 4
(1) 22.5kg of hydroxyl-terminated polyamide-propylene oxide-ethylene oxide copolymerized glycol resin (hydroxyl value is 42mg (KOH)/g) and 10.5kg of isophorone diisocyanate are added into a reaction kettle I, the mixture is heated to 85 ℃ and reacts for 1.2 hours, then 3kg of 1, 2-cyclohexanediol is added to react for 1.5 hours, the temperature is reduced to room temperature, a proper amount of acetone is added to reduce the viscosity of the reactant, 1kg of N- (2-aminoethyl) -aminoethane sodium sulfonate and 5kg of 2, 6-diaminobenzene sodium sulfonate are added, the mixture is stirred and reacts for 0.6 hour at the room temperature, the temperature is increased to 62 ℃, 3kg of epoxy butanol is added to react for 1 hour, and then the polymer is prepared.
(2) And adding 55kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.8 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Example 5
(1) 24kg of hydroxyl-terminated polyamide-tetrahydrofuran-propylene oxide copolymerized glycol resin (hydroxyl value is 56mg (KOH)/g) and 15kg of dimethylene benzene diisocyanate are added into a reaction kettle I, heated to 95 ℃, reacted for 1.5 hours, then 10kg of 1, 3-cyclohexanediol is added for reaction for 1.2 hours, the temperature is reduced to room temperature, a proper amount of acetone is added to reduce the viscosity of reactants, 3kg of sodium ethylene diamine ethanesulfonate is added, stirred at room temperature for reaction for 0.5 hour, heated to 67 ℃, 0.6kg of propylene oxide and 0.4kg of epoxy butanol are added for reaction for 1.4 hours, and then the polymer is prepared.
(2) And adding 47kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 1 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Example 6
(1) 20kg of hydroxyl-terminated polyamide-tetrahydrofuran-ethylene oxide copolymerized glycol resin (hydroxyl value is 40mg (KOH)/g) and 5kg of dicyclohexylmethane diisocyanate are added into a reaction kettle I, heated to 92 ℃, reacted for 1 hour, added with 4kg of 1, 4-cyclohexanediol for reaction for 2 hours, cooled to room temperature, added with a proper amount of acetone to reduce the viscosity of reactants, added with 2kg of 2, 4-diaminobenzene sodium sulfonate, stirred at room temperature for reaction for 0.9 hour, heated to 68 ℃, added with 4kg of epoxy butanol for reaction for 1.5 hours, and then the polymer is prepared.
(2) And adding 65kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.9 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Comparative example 1
An aqueous ink resin was prepared by following the procedure of example 2 except that 27.5kg of the hydroxyl terminated polyamide-polyoxypropylene diol resin was replaced with 27.5kg of poly (terephthalic acid-adipic acid-ethylene glycol-butylene glycol) (general polyester).
Comparative example 2
(1) Adding 15kg of hydroxyl-terminated polyamide-polyoxyethylene glycol resin, 6kg of hydroxyl-terminated polyamide-tetrahydrofuran-propylene oxide copolymerized glycol resin and 13kg of toluene diisocyanate into a reaction kettle I, heating to 80 ℃ for reaction for 2 hours, adding 7kg of 2, 2-dimethyl-1, 3-propanediol for reaction for 1.2 hours, cooling to room temperature, adding a proper amount of acetone to reduce the viscosity of a reactant, adding 10kg of 2- (2-amino-cyclohexylamino) -sodium ethanesulfonate, and stirring at room temperature for reaction for 0.6 hour to obtain the polymer.
(2) And adding 45kg of water into the reaction kettle II, pouring the polymer in the reaction kettle I into the reaction kettle II under the stirring state, continuously stirring and dispersing for 0.5 hour at room temperature, and vacuumizing to remove acetone to obtain the water-based ink resin.
Test example 1
Aqueous inks were prepared, with compositions and contents as given in table 1.
TABLE 1
| Composition of | Content (wt.) |
| (1) Water-based ink resin | 50g |
| (2) Titanium white powder | 17g |
| (3) Dispersant BYK-180 | 0.3g |
| (4) Water (W) | 20g |
The preparation process comprises the following steps: uniformly stirring 25g of water-based ink resin, 17g of titanium dioxide and 0.3g of dispersant BYK-180, grinding the mixture in a sand mill until the fineness of the mixture is less than 15 mu m to prepare color paste, adding the rest 25g of water-based ink resin and 20g of water into the color paste, uniformly stirring, and filtering to prepare the water-based ink.
Preparing a composite packaging base material: the water-based ink resin of example 1 was prepared into water-based ink according to the above water-based ink preparation method, the prepared water-based ink was knife-coated on the surface of a PET film with a wire rod, after drying, two-component polyurethane was used as a coating adhesive, an aluminized film and a PET film were combined, and the ink layer and the two-component polyurethane were located between the PET film and the aluminized film to prepare a composite packaging substrate.
Boiling resistance test: the composite packaging base material is boiled in water at 100 ℃ for 30min, and the PET film and the aluminized film are not layered.
And (3) steaming resistance test: the composite packaging substrate is cooked at 2.321bar (absolute pressure) and 125 deg.C for 30min, and the PET film and the aluminized film are not laminated.
Test examples 2 to 6
Composite packaging substrates were prepared and subjected to retort and retort tests in accordance with the method of test example 1, except that the aqueous ink resins of examples 2-6 were used, and the results were similar to those of test example 1.
Comparative test example 1
A composite packaging substrate was prepared and subjected to the water boiling and boiling resistance tests in accordance with the method of test example 1, except that delamination occurred in the PET film and the aluminum-plated film using the aqueous ink resin of comparative example 1.
Comparative test example 2
A composite packaging substrate was prepared and subjected to the water boiling and boiling resistance tests in accordance with the method of test example 1, except that delamination occurred in the PET film and the aluminum-plated film using the aqueous ink resin of comparative example 2.
As can be seen from the results of test examples 1-6 and comparative examples 1-2, the composite packaging substrate prepared by the water-based ink prepared from the water-based ink resin has the performances of boiling resistance and boiling resistance, and the interlayer peeling phenomenon does not occur. The conventional resin, the comparative example 1 without the hydroxyl-terminated polyamide-ether resin of the present invention, and the comparative example 2 without epoxy alcohol in the step (1) for the end-capping reaction, both showed delamination phenomena in the boiling resistance test and the boiling resistance test, and could not satisfy the boiling resistance and the boiling resistance. Namely, the main structure of the prepared water-based ink resin has good hydrolysis resistance by selecting hydroxyl-terminated polyamide-ether resin as a soft segment and dihydric alcohol as a chain extender; the diamine sulfonate is used as the chain extender, so that the content of hydrophilic components in the water-based ink resin is effectively reduced, and the water resistance of the water-based ink resin is improved. The epoxy group-terminated structure of epoxy alcohol is introduced, so that the adhesion fastness of the ink resin is improved. The water-based ink prepared from the water-based ink resin has the advantages of water boiling resistance and steam boiling resistance after being printed on a packaging base material by the structural characteristics.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The water-based ink composition is characterized by comprising the following components in percentage by weight:
(1) 20-35 wt% of a hydroxyl-terminated polyamide-ether resin;
(2) 5-15 wt% of diisocyanate;
(3) 2-10 wt% of a glycol;
(4) 2-10 wt% of diamine sulfonate;
(5) 1-6 wt% of epoxy alcohol;
(6) 45-65 wt% of water;
the dihydric alcohol is at least one of 2, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, neopentyl glycol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 2-isopropyl-1, 4-butanediol, 3-methyl-1, 5-pentanediol and 2, 4-dimethyl-1, 5-pentanediol.
2. The aqueous ink composition according to claim 1, wherein the hydroxyl-terminated polyamide-ether resin has a hydroxyl value of 28 to 56mg KOH/g.
3. The aqueous ink composition according to claim 1 or 2, wherein the hydroxyl-terminated polyamide-ether resin is at least one of a hydroxyl-terminated polyamide-polyoxyethylene glycol resin, a hydroxyl-terminated polyamide-polyoxypropylene glycol resin, a hydroxyl-terminated polyamide-polytetrahydrofuran glycol resin, a hydroxyl-terminated polyamide-oxypropylene-oxyethylene copolyol resin, a hydroxyl-terminated polyamide-tetrahydrofuran-oxypropylene copolyol resin, a hydroxyl-terminated polyamide-tetrahydrofuran-oxyethylene copolyol resin.
4. The aqueous ink composition according to claim 1, wherein the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate.
5. The aqueous ink composition according to claim 1, wherein the diamine sulfonate is at least one of 2- (2-amino-cyclohexylamino) -ethanesulfonic acid sodium salt, 2- [ (5-amino-1, 3, 3-trimethyl-cyclohexylmethyl) -amino ] -ethanesulfonic acid sodium salt, 2- [4- (4-amino-cyclohexylmethyl) -cyclohexylamino ] -ethanesulfonic acid sodium salt, N- (2-aminoethyl) -aminoethanesulfonic acid sodium salt, ethylenediamine ethanesulfonic acid sodium salt, 2, 4-diaminobenzenesulfonic acid sodium salt, and 2, 6-diaminobenzenesulfonic acid sodium salt.
6. The aqueous ink composition according to claim 1, wherein the epoxy alcohol is propylene oxide and/or butylene oxide.
7. A method for preparing an aqueous ink resin from the aqueous ink composition according to any one of claims 1 to 6, wherein the method comprises the steps of:
(1) carrying out a first reaction on hydroxyl-terminated polyamide-ether resin and diisocyanate, adding dihydric alcohol for a second reaction, cooling to room temperature, adding acetone, then adding diamine sulfonate for a third reaction, and adding epoxy alcohol for a fourth reaction to obtain a polymer;
(2) and (3) contacting the polymer with water to disperse, and removing acetone to obtain the water-based ink resin.
8. The method of claim 7, wherein the conditions of the first reaction comprise: the temperature is 80-100 ℃, and the time is 1-2 h;
the conditions of the second reaction include: the temperature is 80-100 ℃, and the time is 1-2 h;
the conditions of the third reaction include: the temperature is room temperature, and the time is 0.5-1 h;
the conditions of the fourth reaction include: the temperature is 60-70 ℃, and the time is 1-2 h;
the dispersing conditions include: the temperature is room temperature, and the time is 0.5-1 h.
9. An aqueous ink resin prepared by the method of any one of claims 7 to 8.
10. Use of the aqueous ink resin of claim 9 in an ink.
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