CN111471424A - Waterborne polyurethane adhesive and preparation method thereof - Google Patents
Waterborne polyurethane adhesive and preparation method thereof Download PDFInfo
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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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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention provides a water-based polyurethane adhesive and a preparation method thereof. By simultaneously adding the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion into the polyurethane emulsion, the initial viscosity, the hydrolysis resistance and the storage stability of the cured water-based polyurethane adhesive can be effectively improved. If only the aqueous polyacrylic acid emulsion is added, the hydrolysis resistance of the aqueous polyurethane adhesive after curing is not improved, but is easier to hydrolyze; if only the aqueous polycarbonate emulsion is added, the initial viscosity of the aqueous polyurethane adhesive is poor; and simultaneously, the addition of the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion can play a synergistic role: not only effectively improves the initial viscosity of the waterborne polyurethane adhesive, but also has obviously better strength and hydrolysis resistance after curing than the waterborne polyurethane adhesive only added with waterborne polycarbonate emulsion.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a water-based polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive refers to an adhesive containing a urethane group or an isocyanate group in a molecular chain. It is a high molecular material produced by the polymerization reaction of isocyanate group and active hydrogen-containing compound. The adhesive has the characteristics of excellent adhesion, outstanding oil resistance, impact resistance, wear resistance, low temperature resistance and the like, and is widely applied to various fields of automobiles, buildings, wood, furniture, electronics, medicines, national defense and the like.
The solvent-based polyurethane adhesive is a solvent-based adhesive prepared from polyurethane polymers and polyisocyanates as main materials and has the advantages of strong adhesive force, large initial adhesive force, low temperature resistance, wide application range and the like, but the solvent-based polyurethane adhesive can release a large amount of Volatile Organic Compounds (VOC) in a film forming stage and after curing is finished, so that the organic solvent is harmful to human health and pollutes the environment. The waterborne polyurethane adhesive is formed by introducing hydrophilic groups into polyurethane groups and dissolving or dispersing the hydrophilic groups in water, is an environment-friendly industrial adhesive, greatly reduces VOC (volatile organic compounds) emission of finished products, reduces pollution to the environment and harm to human bodies by avoiding the use of organic solvents in raw materials, and simultaneously reduces the risks of flammability and explosiveness in the processes of transportation, storage and use. Therefore, the waterborne polyurethane adhesive becomes the main research and development direction of the current polyurethane adhesive.
Chinese patent document CN110343499A discloses an aqueous adhesive, which comprises 60-80% of aqueous polyurethane emulsion, 0.5-7% of polyurethane modified polyether associative thickener, 10-30% of inorganic filler, 0.05-0.5% of polyether modified polysiloxane wetting agent, 0.05-0.5% of organic silicon modified copolymer type flatting agent, 0.05-0.5% of organic silicon defoaming agent, 0.5-10% of isocyanate curing agent, and the sum of all the components is 100%. The aqueous polyurethane adhesive disclosed in this document has flexibility, abrasion resistance,
The cracking rate is low, the heat resistance is good, and the like, but the initial adhesion effect is poor when the adhesive is applied, and the adhesive is easy to degum; the water resistance of the cured glue is poor, and the defects greatly limit the popularization of the water-based polyurethane adhesive.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor initial viscosity and poor hydrolysis resistance after curing of the water-based polyurethane adhesive in the prior art, thereby providing the water-based polyurethane adhesive and the preparation method thereof.
Therefore, the invention provides the following technical scheme:
the raw materials of the waterborne polyurethane adhesive comprise polyurethane emulsion, waterborne polyacrylic emulsion and waterborne polycarbonate emulsion.
Further, the mass ratio of the aqueous polyacrylic acid emulsion to the aqueous polycarbonate emulsion is (3-7): (1-5).
Furthermore, the raw material of the waterborne polyurethane adhesive also comprises a waterborne polyurethane curing agent.
Further, the waterborne polyurethane curing agent comprises the following components in percentage by mass (3-4): (1-2) the polyisocyanate curing agent and propylene glycol monomethyl ether acetate.
Furthermore, the raw materials of the water-based polyurethane adhesive comprise, by weight, 30-70 parts of polyurethane emulsion, 15-35 parts of water-based polyacrylic acid emulsion and 5-25 parts of water-based polycarbonate emulsion.
Further, the amount of the waterborne polyurethane curing agent is 4.8-9.1 wt% of the total amount of the raw materials.
Further, the raw materials of the waterborne polyurethane adhesive also comprise 0.1-1 part of surface auxiliary agent and 0.5-2 parts of thickening agent;
wherein the surface auxiliary agent is at least one of a water-based organic silicon defoaming agent, a dispersing agent, a flatting agent and a base material wetting agent;
the thickening agent is a polyurethane associative rheological aid.
Furthermore, the raw materials of the waterborne polyurethane adhesive also comprise 0-1 part of pigment; the pigment is at least one of titanium dioxide, carbon black and phthalocyanine blue.
Further, the aqueous polycarbonate emulsion is an anionic polycarbonate dispersion emulsion.
Further, the water-based polyacrylic acid emulsion is water-based polyacrylic acid emulsion which is synthesized by emulsifying an oily vinyl monomer in water and then initiating an initiator;
wherein the oily vinyl monomer is at least one of acrylic acid, methacrylic acid, styrene and derivatives thereof.
Further, the polyurethane emulsion is an aqueous emulsion generated by self-emulsification of an amino-terminated polyurethane prepolymer.
The invention also provides a preparation method of the waterborne polyurethane adhesive, which comprises the following steps:
and uniformly mixing the polyurethane emulsion, the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion to obtain a mixed solution, namely the water-based polyurethane adhesive.
Further, the method also comprises the step of uniformly mixing the mixed solution and the waterborne polyurethane curing agent.
Further, before the mixed liquid and the waterborne polyurethane curing agent are uniformly mixed, the method also comprises the step of uniformly mixing the polyisocyanate curing agent and the propylene glycol monomethyl ether acetate.
Further, the method also comprises the step of mixing the surface auxiliary agent, the polyurethane emulsion, the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion uniformly, and then mixing the mixture with a thickening agent or the thickening agent and a pigment.
The technical scheme of the invention has the following advantages:
1. the raw materials of the waterborne polyurethane adhesive provided by the invention comprise polyurethane emulsion, and further comprise waterborne polyacrylic emulsion and waterborne polycarbonate emulsion. By simultaneously adding the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion into the polyurethane emulsion, the initial viscosity, the hydrolysis resistance and the storage stability of the cured water-based polyurethane adhesive can be effectively improved.
If only the aqueous polyacrylic acid emulsion is added, although the initial viscosity of the aqueous polyurethane adhesive can be improved, the hydrolysis resistance of the cured aqueous polyurethane adhesive is not improved, but the cured aqueous polyurethane adhesive is easier to hydrolyze. The addition of the aqueous polycarbonate emulsion can improve the hydrolysis resistance of the aqueous polyurethane adhesive after curing, but the initial tack is poor. And simultaneously, the addition of the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion can play a synergistic role: not only effectively improves the initial viscosity of the waterborne polyurethane adhesive, but also has obviously better strength and hydrolysis resistance after curing than the waterborne polyurethane adhesive only added with waterborne polycarbonate emulsion.
2. According to the waterborne polyurethane adhesive provided by the invention, the initial viscosity, hydrolysis resistance after curing and storage stability of the waterborne polyurethane adhesive can be further improved by limiting the mass ratio of the waterborne polyacrylic emulsion to the waterborne polycarbonate emulsion.
3. The waterborne polyurethane adhesive provided by the invention can further improve the curing performance, hydrolysis resistance and storage stability after curing of the waterborne polyurethane adhesive by adding the waterborne polyurethane curing agent.
4. According to the waterborne polyurethane adhesive provided by the invention, the mixture of the polyisocyanate curing agent and the propylene glycol monomethyl ether acetate is used as the curing agent, and the mass ratio of the polyisocyanate curing agent to the propylene glycol monomethyl ether acetate is limited, so that the gloss, the hardness and the adhesive force of the waterborne polyurethane adhesive and the hydrolysis resistance after curing can be further improved.
5. The initial viscosity, hydrolysis resistance and storage stability of the waterborne polyurethane adhesive after curing can be further improved by limiting the parts of the raw materials and the using amount of the waterborne polyurethane curing agent.
6. The surface auxiliary agent and the thickening agent are added to the waterborne polyurethane adhesive provided by the invention, so that the film forming property and the gloss property of the waterborne polyurethane adhesive can be improved, and the initial viscosity and the hydrolysis resistance after curing of the waterborne polyurethane adhesive can be further improved.
7. The aqueous polyurethane adhesive provided by the invention can further improve the stability of the aqueous polyurethane adhesive by further limiting the aqueous polycarbonate emulsion to be the anionic polycarbonate dispersion emulsion.
8. The waterborne polyurethane adhesive provided by the invention can further improve the initial viscosity of the waterborne polyurethane adhesive by further limiting the oily vinyl monomer for synthesizing the acrylic emulsion to be acrylic acid, methacrylic acid, styrene and derivatives thereof.
9. According to the water-based polyurethane adhesive provided by the invention, the strength and hydrolysis resistance of the water-based polyurethane adhesive after curing can be further improved by further limiting the polyurethane emulsion to be water emulsion generated by self-emulsification of the amino-terminated polyurethane prepolymer.
10. The preparation method of the waterborne polyurethane adhesive provided by the invention is simple and convenient, and the prepared waterborne polyurethane adhesive has excellent initial adhesion, cured strength, hydrolysis resistance and storage stability.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In the technical scheme of the invention, all raw materials are prepared from commercially available products or existing synthetic methods and can meet the implementation of the technical scheme of the invention, but in order to facilitate the comparison between each embodiment and a comparative example, the polyurethane emulsion adopts the aqueous polyurethane emulsion with the model number of U53 sold by Corsia polymer (China) Co., Ltd, and the aqueous polyacrylic acid emulsion adopts the aqueous acrylic resin with the model number of NeoCryyl XK-12 sold by Dissman (China) Co., Ltd; the aqueous polycarbonate emulsion adopts polycarbonate type aqueous polyurethane dispersion sold by Corssian Polymer (China) Limited and with the model number of Bayhydrol UH-2888; the polyisocyanate curing agent was a type Desmodur RN curing agent sold by Corcission Polymer (China) Co.
The polyurethane associative rheology additives are all aqueous solutions of 10 wt% strength formulated with a hydroxyethyl cellulose aqueous thickener manufactured by the Ashland group, part number NATROSO L Performax.
The defoaming agent is a model SD-670 defoaming agent sold by Wake (China) Co; the dispersant is KYC-9366 dispersant sold by Hangzhou Keying chemical company Limited; the leveling agent is sold by Hangzhou Keying chemical company limited and is of a model number KYC-616; the substrate wetting agent was a substrate wetting agent sold by Kh-560 available from Chengdu silicon technologies, Inc.
Example 1
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 60kg of polyurethane emulsion, 15kg of water-based polyacrylic acid emulsion, 15kg of water-based polycarbonate emulsion, 0.2kg of defoaming agent, 0.1kg of dispersing agent, 0.1kg of flatting agent and 0.1kg of base material wetting agent at the stirring speed of 500r/min for 20min at room temperature; then under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive and 0.2kg of phthalocyanine blue are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 10:1 to obtain the waterborne polyurethane adhesive.
Example 2
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 50kg of polyurethane emulsion, 25kg of water-based polyacrylic acid emulsion, 20kg of water-based polycarbonate emulsion, 0.2kg of defoaming agent, 0.1kg of dispersing agent, 0.1kg of flatting agent and 0.1kg of base material wetting agent at the stirring speed of 500r/min for 30min at room temperature; then, under the stirring speed, 3.3kg of deionized water, 1kg of polyurethane associative rheological additive and 0.2kg of carbon black are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 20:1 to obtain the waterborne polyurethane adhesive.
Example 3
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 50kg of polyurethane emulsion, 15kg of water-based polyacrylic acid emulsion, 25kg of water-based polycarbonate emulsion, 0.4kg of defoaming agent, 0.2kg of dispersing agent, 0.2kg of flatting agent and 0.2kg of base material wetting agent at the stirring speed of 500r/min for 25min at room temperature; then, under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associative rheological additive and 0.2kg of titanium dioxide are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 15:1 to obtain the waterborne polyurethane adhesive.
Example 4
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 70kg of polyurethane emulsion, 20kg of water-based polyacrylic acid emulsion, 5kg of water-based polycarbonate emulsion, 0.4kg of defoaming agent, 0.3kg of dispersing agent and 0.3kg of flatting agent at the stirring speed of 500r/min for 20min at room temperature; then under the stirring speed, adding 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive, 0.5kg of phthalocyanine blue and 0.5kg of titanium dioxide to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 20:1 to obtain the waterborne polyurethane adhesive.
Example 5
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 35kg of polyurethane emulsion, 35kg of water-based polyacrylic acid emulsion, 25kg of water-based polycarbonate emulsion, 0.4kg of defoaming agent, 0.2kg of dispersing agent, 0.2kg of flatting agent and 0.2kg of base material wetting agent at the stirring speed of 500r/min for 20min at room temperature; then under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive and 0.5kg of phthalocyanine blue are added to obtain a mixed solution;
mixing and stirring 60kg of polyisocyanate curing agent (Desmodur RN) and 40kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 15:1 to obtain the waterborne polyurethane adhesive.
Example 6
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 30kg of polyurethane emulsion, 30kg of water-based polyacrylic acid emulsion, 10kg of water-based polycarbonate emulsion and 0.1kg of defoaming agent at the stirring speed of 500r/min for 20min at room temperature; then, under the stirring speed, 8.8kg of deionized water and 2kg of polyurethane associated rheological additive are added to obtain mixed solution;
mixing and stirring 70kg of polyisocyanate curing agent (Desmodur RN) and 30kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 12:1 to obtain the waterborne polyurethane adhesive.
Example 7
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 50kg of polyurethane emulsion, 25kg of water-based polyacrylic acid emulsion, 20kg of water-based polycarbonate emulsion, 0.3kg of defoaming agent and 0.2kg of dispersing agent at the stirring speed of 500r/min for 30min at room temperature; then, under the stirring speed, 3.3kg of deionized water and 1kg of polyurethane associated rheological additive are added to obtain mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 20:1 to obtain the waterborne polyurethane adhesive.
Example 8
This embodiment provides an aqueous polyurethane adhesive, which is prepared by the following steps:
mixing and stirring 60kg of polyurethane emulsion, 35kg of water-based polyacrylic acid emulsion, 5kg of water-based polycarbonate emulsion, 0.2kg of defoaming agent, 0.1kg of dispersing agent, 0.1kg of flatting agent and 0.1kg of base material wetting agent at the stirring speed of 500r/min for 20min at room temperature; then under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive and 0.2kg of phthalocyanine blue are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 10:1 to obtain the waterborne polyurethane adhesive.
Comparative example 1
The comparative example provides an aqueous polyurethane adhesive, which is prepared by the following method:
mixing and stirring 60kg of polyurethane emulsion, 15kg of water-based polycarbonate emulsion, 0.2kg of watt-gram SD-670 defoaming agent, 0.1kg of dispersing agent, 0.1kg of flatting agent and 0.1kg of base material wetting agent for 20min at the stirring speed of 500r/min at room temperature; then under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive and 0.2kg of phthalocyanine blue are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 10:1 to obtain the waterborne polyurethane adhesive.
Comparative example 2
The comparative example provides an aqueous polyurethane adhesive, which is prepared by the following method:
mixing and stirring 60kg of polyurethane emulsion, 15kg of water-based polyacrylic acid emulsion, 0.2kg of watt-gram SD-670 defoaming agent, 0.1kg of dispersing agent, 0.1kg of flatting agent and 0.1kg of base material wetting agent at the stirring speed of 500r/min for 20min at room temperature; then under the stirring speed, 8.8kg of deionized water, 0.5kg of polyurethane associated rheological additive and 0.2kg of phthalocyanine blue are added to obtain a mixed solution;
mixing and stirring 80kg of polyisocyanate curing agent (Desmodur RN) and 20kg of propylene glycol monomethyl ether acetate for 4 hours at the temperature of 60 ℃ and the stirring speed of 800r/min to obtain the waterborne polyurethane curing agent;
and uniformly mixing the mixed solution and the waterborne polyurethane curing agent according to the mass ratio of 10:1 to obtain the waterborne polyurethane adhesive.
Examples of the experiments
The aqueous polyurethane adhesives prepared in the above examples and comparative examples were tested for initial adhesion strength, peel strength after complete curing, and peel strength after storage for 7 days at 70 ℃ and 50% humidity, respectively, and the specific test results are shown in table 1; wherein the initial adhesion strength is characterized by the peel strength directly measured 15min after bonding is completed, and the initial adhesion strength and the peel strength are both measured according to the test method of GBT 2791-1995.
TABLE 1 test results of aqueous polyurethane adhesives obtained in examples and comparative examples
The data in the table show that the initial adhesive strength of the prepared waterborne polyurethane adhesive can be obviously improved by the waterborne polyacrylic emulsion; the water-based polycarbonate emulsion can improve the complete curing strength, and the strength after high-temperature and high-humidity treatment is obviously improved. According to the invention, the initial viscosity, the hydrolysis resistance and the storage stability after curing of the waterborne polyurethane adhesive can be effectively improved by simultaneously adding the waterborne polyacrylic emulsion and the waterborne polycarbonate emulsion into the polyurethane emulsion.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (15)
1. The raw materials of the waterborne polyurethane adhesive comprise polyurethane emulsion, and the waterborne polyurethane adhesive is characterized by also comprising waterborne polyacrylic emulsion and waterborne polycarbonate emulsion.
2. The aqueous polyurethane adhesive of claim 1, wherein the mass ratio of the aqueous polyacrylic emulsion to the aqueous polycarbonate emulsion is 3-7: 1-5.
3. The waterborne polyurethane adhesive of claim 1 or 2, further comprising a waterborne polyurethane curing agent.
4. The waterborne polyurethane adhesive of claim 3, wherein the waterborne polyurethane curing agent comprises the following components in a mass ratio of 3-4: 1-2 polyisocyanate curing agent and propylene glycol methyl ether acetate.
5. The waterborne polyurethane adhesive of any one of claims 1 to 4, wherein the raw materials comprise, by weight, 30 to 70 parts of a polyurethane emulsion, 15 to 35 parts of a waterborne polyacrylic acid emulsion, and 5 to 25 parts of a waterborne polycarbonate emulsion.
6. The waterborne polyurethane adhesive of any one of claims 3 to 5, wherein the amount of the waterborne polyurethane curing agent is 4.8 to 9.1 wt% of the total amount of the raw materials.
7. The aqueous polyurethane adhesive according to claim 5 or 6, wherein the raw materials further comprise 0.1-1 part of a surface auxiliary agent and 0.5-2 parts of a thickener;
wherein the surface auxiliary agent is at least one of a water-based organic silicon defoaming agent, a dispersing agent, a flatting agent and a base material wetting agent;
the thickening agent is a polyurethane associative rheological aid.
8. The waterborne polyurethane adhesive of any one of claims 5-7, wherein the raw materials further comprise 0-1 part of a pigment; the pigment is at least one of titanium dioxide, carbon black and phthalocyanine blue.
9. The aqueous polyurethane adhesive of any one of claims 1-8, wherein the aqueous polycarbonate emulsion is an anionic polycarbonate dispersion emulsion.
10. The aqueous polyurethane adhesive of any one of claims 1-9, wherein the aqueous polyacrylic acid emulsion is an aqueous polyacrylic acid emulsion synthesized by emulsifying an oily vinyl monomer in water and then initiating an initiator;
wherein the oily vinyl monomer is at least one of acrylic acid, methacrylic acid, styrene and derivatives thereof.
11. The aqueous polyurethane adhesive of any one of claims 1-10, wherein the polyurethane emulsion is an aqueous emulsion of an amino-terminated polyurethane prepolymer produced by self-emulsification.
12. The preparation method of the water-based polyurethane adhesive is characterized by comprising the following steps:
and uniformly mixing the polyurethane emulsion, the water-based polyacrylic acid emulsion and the water-based polycarbonate emulsion to obtain a mixed solution, namely the water-based polyurethane adhesive.
13. The method for preparing the waterborne polyurethane adhesive according to claim 12, further comprising the step of uniformly mixing the mixed solution with the waterborne polyurethane curing agent.
14. The method of claim 13, further comprising the step of mixing the polyisocyanate curing agent and the propylene glycol methyl ether acetate uniformly before mixing the mixture and the aqueous polyurethane curing agent uniformly.
15. The method for preparing the aqueous polyurethane adhesive according to any one of claims 1 to 14, further comprising the step of mixing the surface auxiliary agent with the polyurethane emulsion, the aqueous polyacrylic acid emulsion and the aqueous polycarbonate emulsion, and then mixing with the thickener or the thickener and the colorant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112608665A (en) * | 2020-11-11 | 2021-04-06 | 沪宝新材料科技（上海）股份有限公司 | Aging-resistant PC interface agent |
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|---|---|---|---|---|
| CN101407704A (en) * | 2008-11-14 | 2009-04-15 | 上海维凯化学品有限公司 | Environment-friendly type aqueous heat sealing glue for medicament blister package and use thereof |
| CN101967255A (en) * | 2010-09-21 | 2011-02-09 | 大连市轻化工研究所 | Waterborne resin for plastic film coating and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407704A (en) * | 2008-11-14 | 2009-04-15 | 上海维凯化学品有限公司 | Environment-friendly type aqueous heat sealing glue for medicament blister package and use thereof |
| CN101967255A (en) * | 2010-09-21 | 2011-02-09 | 大连市轻化工研究所 | Waterborne resin for plastic film coating and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112608665A (en) * | 2020-11-11 | 2021-04-06 | 沪宝新材料科技（上海）股份有限公司 | Aging-resistant PC interface agent |
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