CN112831306A - Anti-yellowing aqueous adhesive and preparation method and application thereof - Google Patents
Anti-yellowing aqueous adhesive and preparation method and application thereof Download PDFInfo
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
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- -1 polyoxyethylene Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of adhesives, and discloses a yellowing-resistant water-based adhesive as well as a preparation method and application thereof. The yellowing-resistant water-based adhesive comprises the following components: the water-based polyurethane emulsion comprises water-based polyurethane emulsion, a defoaming agent, a plasticizer, a cross-linking agent, a thickening agent and a surfactant. The invention solves the problem of wettability of the existing sewing flanging adhesive by adding the organic silicon defoamer and the surfactant; the adhesive force and the strength of the adhesive are changed by adding a cross-linking agent; the viscosity is increased by a thickener.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a yellowing-resistant water-based adhesive as well as a preparation method and application thereof.
Background
The common adhesives used for sewing hems of shoes and bags in the market are oily neoprene adhesive and water-based neoprene adhesive. The oily neoprene contains high TVOC (total volatile organic compounds), and the emission of organic solvent can cause the waste of resources, the pollution of the environment and the damage to the health of direct contact persons. The oily chloroprene adhesive is poor in yellowing resistance, has pungent solvent smell and has a flammable risk.
With the rising price of raw materials such as neoprene sheets and organic solvents, the cost of the oily stitching and edge folding glue is higher and higher. When the oily sewing machine edge folding glue is produced, stirring and dissolving are needed for 2-4 hours, heating is carried out, the oily sewing machine edge folding glue is reacted for 4-6 hours at the temperature of 60-90 ℃, the total production time is 8-12 hours, the production time is long, the energy consumption is high, the production efficiency is low, and the risk of explosion caused by overhigh temperature and pressure in a stirring kettle exists. The aqueous neoprene adhesive has high cost, poor yellowing resistance and general adhesive property.
At present, domestic high-quality environment-friendly water-based polyurethane adhesives for shoes are rare in the market, and the main reason is that a large amount of water needs to be removed for a long time during use, so that the use efficiency of the water-based polyurethane adhesives is reduced. Moreover, the existing waterborne polyurethane adhesive film is hard and cannot be directly used for stitching and folding edges.
Therefore, the development of an environment-friendly aqueous polyurethane adhesive for shoes is urgently needed, and the problems of yellowing of the stitching edge adhesive and hard adhesive film are solved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the yellowing-resistant aqueous adhesive, and the preparation method and the application thereof, the aqueous adhesive can solve the problems of yellowing of the stitching edge-folding adhesive and hard adhesive film, has zero TVOC (total volatile organic compound) emission, has no pollution to the atmospheric environment, and has little harm to the health of direct contact persons.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aqueous adhesive comprises the following components: the water-based polyurethane emulsion, the organic silicon defoamer and the cross-linking agent; the crosslinking agent is at least one of a carbodiimide type crosslinking agent or aliphatic polyisocyanate.
Preferably, the aqueous adhesive further comprises the following components: at least one of a plasticizer, a thickener, or a surfactant.
Preferably, the aqueous adhesive comprises the following components in parts by weight: 100 portions of aqueous polyurethane emulsion, 0.01 to 1 portion of defoaming agent, 5 to 20 portions of plasticizer, 0.05 to 5 portions of cross-linking agent, 0.1 to 5 portions of thickening agent and 0.05 to 0.5 portion of surfactant.
Preferably, the aqueous polyurethane emulsion is a milky white liquid, the solid content is 40-60%, the viscosity is 30-300 cps at 25 ℃, the pH is 7-9, and the content of the organic solvent is 0-10%.
Preferably, the silicone defoamer is a polyether modified silicone defoamer; more preferably, the polyether modified silicone defoamer is polyether alkylphenol polyoxyethylene ether.
The nonionic surface active defoaming agent (organic silicon defoaming agent) can be used as a defoaming agent and a surfactant, has hydrophilicity, wetting and defoaming, and also solves the problem of poor wettability of the existing sewing flanging adhesive.
Preferably, the plasticizer is a benzoate plasticizer; the benzoate plasticizer is at least one of dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, diethylene glycol dibenzoate or dipropylene glycol dibenzoate.
Preferably, the aliphatic polyisocyanate is one of aliphatic polyisocyanate DesmodurDA or aliphatic polyisocyanate DesmodurDN.
Preferably, the carbodiimide-type crosslinking agent is at least one of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide, or polycarbodiimide.
Polycarbodiimide does not contain VOC, reacts with carboxyl to crosslink, and can crosslink at normal temperature (because shoes can not be processed at high temperature, crosslinking is carried out at normal temperature); suitable for use in aqueous systems. The addition of 5-10% to the carboxyl group-containing polymer can increase: water resistance, chemical resistance, wear resistance, stain resistance, improved adhesion to special substrates, crosslinking at room temperature, and no need of nitrogen gas protection for the crosslinking agent.
Preferably, the thickener is a polyurethane associative thickener; the polyurethane associative thickener Vesmody U601 or Borchi Gel 0625. Polyurethane associative thickener: HEUR for short, is a hydrophobic group modified polyurethane water-soluble polymer, and belongs to a nonionic associative thickener. Vesmody U601 (a Wanhua polyurethane associative thickener) has a solids content of 35%, a viscosity of 30000-38000 cps. The Vesmody U601 efficient pseudoplastic non-ionic polyurethane thickener can greatly improve the medium and low shear viscosity of a formula and has excellent leveling and sagging prevention balance. The thickening agent is suitable for thickening any aqueous system, and is particularly suitable for being applied to aqueous adhesives.
The Borchi Gel 0625 is a universal pseudoplastic polyurethane thickener, has 25 percent of PU content and 50 percent of solid content, does not contain solvent, APEO, HAPS and organic tin, and is suitable for the range of medium-high shear rate (1000-10000 rps).
Preferably, the surfactant is one of sodium dodecyl sulfate or alkylphenol polyoxyethylene.
A preparation method of an aqueous adhesive comprises the following steps:
(1) adding an organic silicon defoaming agent into the aqueous polyurethane emulsion, stirring, adding a plasticizer, a cross-linking agent and a surfactant, and continuously stirring to obtain a mixed solution;
(2) and (2) adding a thickening agent into the mixed solution prepared in the step (1) for several times, and stirring to obtain the aqueous adhesive.
Preferably, the step (1) further comprises mixing the aqueous polyurethane and a solvent to obtain an aqueous polyurethane emulsion.
More preferably, the solvent is one of water, ethanol and propanol.
Preferably, in the step (1), the stirring time is 10-20min, the temperature is 20-40 ℃, and the continuous stirring time is 10-30 min.
Preferably, in the step (1), the stirring speed is increased to 250-500 rpm.
Preferably, in step (1), the reduced stirring speed is 10 to 200 rpm.
Preferably, in step (1), the number of times is 3 to 10 times.
The invention also provides application of the water-based adhesive in preparation of shoes or bags.
Has the advantages that:
1. the invention solves the problem of wettability of the existing sewing flanging adhesive by adding the organic silicon defoaming agent; and then the advantages of the cross-linking agent and the waterborne polyurethane are complemented, so that the adhesive is cross-linked from a linear structure into a net structure, the adhesive force and the strength of the adhesive are increased, and particularly, the polycarbodiimide is used, so that the adhesive can achieve the water resistance, the chemical resistance, the wear resistance, the stain resistance and the light resistance, and has good film characteristics and water solubility.
2. The main medium of the aqueous polyurethane emulsion is water, zero TVOC (total volatile organic compound) emission is realized, no pollution is caused to the atmospheric environment, and the harm to the health of direct contact persons is slight.
3. When the yellowing-resistant aqueous adhesive is prepared, the yellowing-resistant aqueous adhesive is stirred at normal temperature without heating and dissolving reaction, the energy consumption is low, the production time is shortened to 2-4 hours, the production efficiency is high, and the risk of explosion is avoided.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a graph showing yellowing test results of aqueous adhesives prepared in example 1 and comparative examples 1-2;
FIG. 2 is a graph of the results of a comparative tack hold time test of the aqueous adhesives prepared in example 1 and comparative examples 1-2;
FIG. 3 is a graph of the results of comparative tests of the tack heat resistance of the aqueous adhesives prepared in example 1 and comparative examples 1-2.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The yellowing-resistant aqueous adhesive comprises the following components in parts by weight: 100 parts of aqueous polyurethane resin, 0.05 part of polyether alkylphenol polyoxyethylene ether, 5 parts of dibutyl terephthalate, 5 parts of butyl (2-ethylhexyl) terephthalate, 0.2 part of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.5 part of polyurethane associated thickener Vesmody U601, 0.1 part of sodium dodecyl sulfate and 0.2 part of alkylphenol polyoxyethylene ether.
The embodiment prepares the yellowing-resistant aqueous adhesive, and the specific process comprises the following steps:
(1) preparing an aqueous polyurethane emulsion: mixing waterborne polyurethane and a solvent to obtain waterborne polyurethane emulsion;
(2) adding polyether alkylphenol polyoxyethylene ether into the aqueous polyurethane emulsion, stirring for 10 minutes, adding dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium dodecyl sulfate and alkylphenol polyoxyethylene ether, increasing the stirring speed to 250-500 r/min, and stirring for 15 minutes to obtain a mixed solution;
(3) and reducing the stirring speed to 100 r/min, adding the polyurethane associative thickener Vesmody U601 into the mixed solution for 8 times, and stirring for 30min until the viscosity is 20000 cps-30000 cps, thus obtaining the yellowing-resistant water-based adhesive.
Example 2
The yellowing-resistant aqueous adhesive comprises the following components in parts by weight: 100 parts of aqueous polyurethane resin, 0.05 part of polyether alkylphenol polyoxyethylene ether, 10 parts of dibutyl terephthalate, 10 parts of butyl (2-ethylhexyl) terephthalate, 0.2 part of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.5 part of polyurethane associated thickener Vesmody U601, 0.1 part of sodium dodecyl sulfate and 0.2 part of alkylphenol polyoxyethylene ether.
The embodiment prepares the yellowing-resistant aqueous adhesive, and the specific process comprises the following steps:
(1) preparing an aqueous polyurethane emulsion: mixing waterborne polyurethane and a solvent to obtain waterborne polyurethane emulsion;
(2) adding polyether alkylphenol polyoxyethylene ether into the aqueous polyurethane emulsion, stirring for 10 minutes, adding dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium dodecyl sulfate and alkylphenol polyoxyethylene ether, increasing the stirring speed to 250-500 r/min, and stirring for 15 minutes to obtain a mixed solution;
(3) and reducing the stirring speed to 100 r/min, adding the polyurethane associative thickener Vesmody U601 into the mixed solution for 8 times, and stirring for 30min until the viscosity is 8000 cps-10000 cps, thus obtaining the yellowing-resistant waterborne adhesive.
Example 3
The yellowing-resistant aqueous adhesive comprises the following components in parts by weight: 100 parts of aqueous polyurethane resin, 0.05 part of polyether alkylphenol polyoxyethylene ether, 2 parts of dibutyl terephthalate, 3 parts of butyl (2-ethylhexyl) terephthalate, 0.2 part of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.5 part of polyurethane associated thickener Vesmody U601, 0.1 part of sodium dodecyl sulfate and 0.2 part of alkylphenol polyoxyethylene ether.
The embodiment prepares the yellowing-resistant aqueous adhesive, and the specific process comprises the following steps:
(1) preparing an aqueous polyurethane emulsion: mixing waterborne polyurethane and a solvent to obtain waterborne polyurethane emulsion;
(2) adding polyether alkylphenol polyoxyethylene ether into the aqueous polyurethane emulsion, stirring for 10 minutes, adding dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium dodecyl sulfate and alkylphenol polyoxyethylene ether, increasing the stirring speed to 250-500 r/min, and stirring for 15 minutes to obtain a mixed solution;
(3) and reducing the stirring speed to 100 r/min, adding the polyurethane associative thickener Vesmody U601 into the mixed solution for 6 times, and stirring for 30min until the viscosity is 10000-20000 cps, thus obtaining the yellowing-resistant water-based adhesive.
Comparative example 1
The specific preparation process of the oily neoprene adhesive of the comparative example is as follows:
(1) adding toluene into a reaction kettle with a condensation reflux device, starting stirring, adding the chloroprene rubber sheet, and heating to 50-60 ℃ to completely dissolve the chloroprene rubber sheet.
(2) And (3) when the chloroprene rubber sheet is completely dissolved and then the temperature is raised to 85-90 ℃, adding methyl methacrylate and benzoyl peroxide into the reaction kettle, keeping the temperature in the reaction kettle at 88-90 ℃, and reacting for 3-4 hours.
(3) And (3) starting sampling to measure the viscosity after reacting for 3 hours, measuring once per hour, stopping reacting and starting cooling when the viscosity reaches 8000-10000 cps, adding terminating agents of hydroquinone and rosin resin when the temperature reaches 40 ℃, stirring for 10-20 minutes, stopping, inspecting, discharging and packaging.
Comparative example 2
The embodiment prepares the water-based chloroprene rubber adhesive, and the specific process comprises the following steps:
(1) weighing 100g of high-crystallization-rate water-based neoprene emulsion, and adding methanol to obtain water-based neoprene emulsion;
(2) adding polyether alkylphenol polyoxyethylene into the water-based neoprene emulsion, stirring for 10 minutes, adding dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium dodecyl sulfate and alkylphenol polyoxyethylene, increasing the stirring speed to 250-500 revolutions per minute, and stirring for 15 minutes to obtain a mixed solution;
(3) reducing the stirring speed to 100 r/min, adding the polyurethane associative thickener Vesmody U601 into the mixed solution for multiple times, and stirring for 30min until the viscosity is 20000 cps-30000 cps, thus obtaining the water-based chloroprene adhesive.
The using method comprises the following steps: the yellowing-resistant aqueous adhesives of the examples 1-3 and the chloroprene adhesives of the comparative examples 1-2 are coated on the surfaces of materials such as leather, canvas and sponge by using a hairbrush, placed at room temperature for 5-10 minutes and then attached and pressurized, or attached and pressurized in an oven at 50-60 ℃ for 3-4 minutes.
Test examples
Yellowing test:
testing an instrument: QUV/se machine irradiation, datacolor 600.
The test method comprises the following steps: the adhesive is coated on the surface of white canvas, the yellowing-resistant water-based adhesive prepared in examples 1-3 and the water-based chloroprene adhesive prepared in comparative example 2 are placed in an oven 4 '30 ℃ at 70 ℃, and the oil-based chloroprene adhesive prepared in comparative example 1 is placed in an oven 2' 30 ℃ at 70 ℃ and dried.
And (3) testing conditions are as follows: the radiation was irradiated for 24 hours by a QUV/se machine and the yellowing rating was measured by a datacolor 600.
The test results are shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Yellowing grade | 4.5 | 4.4 | 4.6 | 2.5 | 2.0 |
Note: the yellowing grade is 0-5, and the smaller the numerical value is, the more yellow the adhesive film is, the worse the yellowing is.
FIG. 1 is a graph showing yellowing test results of example 1 and comparative examples 1-2, wherein the yellowing grade of the aqueous adhesive prepared in example 1 of the present invention is 4.5, the yellowing grade of the oily neoprene is 2.5, and the yellowing grade of the aqueous neoprene is 2.0, which illustrates that the yellowing resistance of the product of the present invention is the best.
Wet stick tack hold time test
Testing materials: 1cm2The screen cloth and the leather.
The test method comprises the following steps: coating adhesive on the mesh or leather, standing at room temperature (25 deg.C) for 1 min, 5 min, 10 min, and 15 min, sticking the mesh or leather with the adhesive, and slightly pressing (pressure of 2 kg/cm)2) And observing whether the material can be bounced open or not.
FIG. 2 is a graph of the results of the test comparing the adhesive holding times of example 1 and comparative examples 1-2, the results of the test being: the yellowing-resistant aqueous adhesive and the oily neoprene adhesive prepared in the embodiment 1 of the invention can be bonded in 1 minute, the materials do not bounce, and the bonding time is more than 30 minutes. And (3) attaching the water-based neoprene adhesive for 1 minute, popping the mesh fabric and the leather material, attaching the cloth fabric and the leather material for 5 minutes, popping the mesh fabric material, and not popping the leather material. The wet-sticking viscosity maintaining time of the yellowing-resistant aqueous adhesive prepared in the embodiment 1 of the invention is the same as that of oily neoprene adhesive, and is better than that of aqueous neoprene adhesive.
Heat resistance test
Testing materials: 1cm2The screen cloth and the leather.
The test method comprises the following steps: the yellowing-resistant aqueous adhesives prepared in examples 1-3 and the adhesives prepared in comparative examples 1-2 were coated on the surfaces of a mesh and leather, and left at room temperature (25 ℃) for 1 minute, 5 minutes, 10 minutes and 15 minutes, the mesh or leather was faced with the adhesive coated thereon, and the pressure was lightly pressed (pressure of 2 kg/cm)2) And observing whether the material can be bounced open or not.
And (3) testing conditions are as follows: the pressed material was placed in an oven at 70 ℃ for 10 minutes and the distance the material bounced off was observed.
And (3) testing results: the materials of the yellowing-resistant aqueous adhesive prepared in the embodiments 1 to 3 of the invention do not pop open, the mesh material with the oily neoprene pops open, the leather partially pops open, and the mesh material with the aqueous neoprene pops open, and the leather partially pops open. The yellowing-resistant water-based adhesive prepared in the embodiments 1 to 3 of the invention has better heat resistance than oil-based neoprene and water-based neoprene. FIG. 3 is a graph showing the results of comparative tests on the viscosity and heat resistance of the adhesive prepared in example 1 and comparative examples 1-2, wherein the materials of the yellowing-resistant aqueous adhesive prepared in example 1 of the present invention do not pop open, the mesh material with oily neoprene pops open, the leather partially pops open, the mesh material with aqueous neoprene pops open, and the leather partially pops open.
Testing the membrane performance:
the yellowing-resistant aqueous adhesives prepared in examples 1-3 and the adhesives prepared in comparative examples 1-2 are prepared into films.
Preparation of film samples: the yellowing-resistant aqueous adhesive prepared in examples 1-3 and the adhesive prepared in comparative examples 1-2 are coated on the surfaces of mesh cloth and leather, placed at room temperature (25 ℃) for 1 hour, 5 hours, 10 hours and 15 hours, placed in a vacuum oven, dried at 50 ℃ in vacuum to constant weight, taken out and placed in a dryer for later use.
Table 2 shows the results of the adhesive film performance test in comparative examples 1-2 and examples 1-3:
as can be seen from table 2, the comparative example 1 has the lowest hardness, but has a poor tensile force and does not meet the standard of stitching, whereas the aqueous neoprene adhesive of the comparative example 2 has a poor tensile force, has a high hardness and does not meet the standard of stitching although the aqueous adhesive has. The embodiment 1-3 of the invention has moderate hardness and large tension, namely high viscosity, completely meets the standard of sewing and edge folding, and can be used for preparing shoes and bags.
As can be seen from Table 2, the films of examples 1 to 3 of the present invention have good flexibility, good hardness and tack properties, and good tensile strength and bending resistance. The adhesive film prepared in examples 1-3 has good viscosity, which is 20000-22000 cps.
And (3) testing tension:
examples 1, 2, 3, comparative example 2 were painted onto canvas 10cm (long) × 2.5cm (wide), placed in an oven 4 '30 "at 70 ℃, taken out and painted again, placed in an oven 4' 30" at 70 ℃, faced with an adhesive and pressed with a pressure of 20kg for 8 seconds.
Comparative example 1 was painted onto 10cm (length) × 2.5cm (width) canvas, placed in 70 ℃ oven 2 '30 ", taken out again and painted, placed in 70 ℃ oven 2' 30", with the adhesive-coated face facing, and pressed with 20kg pressure for 8 seconds.
The instrument is Kejian KJ-106A, the tensile force is tested, the result is shown in Table 2, the tensile force of the example 1 can reach 6.2kg/cm2。
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The water-based adhesive is characterized by comprising the following components: the water-based polyurethane emulsion, the organic silicon defoamer and the cross-linking agent; the crosslinking agent is at least one of a carbodiimide type crosslinking agent or aliphatic polyisocyanate.
2. The aqueous adhesive of claim 1, further comprising the following components: at least one of a plasticizer, a thickener, or a surfactant.
3. The aqueous adhesive according to claim 2, characterized by comprising the following components in parts by weight: 100 portions of aqueous polyurethane emulsion, 0.01 to 1 portion of defoaming agent, 5 to 20 portions of plasticizer, 0.05 to 5 portions of cross-linking agent, 0.1 to 5 portions of thickening agent and 0.05 to 0.5 portion of surfactant.
4. The aqueous adhesive as claimed in claim 1, wherein the aqueous polyurethane emulsion has a solid content of 40-60%, a viscosity of 30-300 cps at 25 ℃, a pH of 7-9, and an organic solvent content of 0-10%.
5. The aqueous adhesive of claim 1 wherein the silicone defoamer is a polyether modified silicone defoamer; the polyether modified organic silicon defoaming agent is polyether alkylphenol polyoxyethylene ether.
6. The aqueous adhesive of claim 2 wherein the plasticizer is a benzoate plasticizer; the benzoate plasticizer is at least one of dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, diethylene glycol dibenzoate or dipropylene glycol dibenzoate.
7. The aqueous adhesive of claim 1 wherein the carbodiimide-type crosslinker is at least one of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N' -diisopropylcarbodiimide, or polycarbodiimide.
8. The aqueous adhesive of claim 2 wherein the thickener is a polyurethane associative thickener; the surfactant is one of sodium dodecyl sulfate or alkylphenol polyoxyethylene.
9. The method for preparing the aqueous adhesive according to any one of claims 2 to 8, which is characterized by comprising the following steps:
(1) adding an organic silicon defoaming agent into the aqueous polyurethane emulsion, stirring, adding a plasticizer, a cross-linking agent and a surfactant, and continuously stirring to obtain a mixed solution;
(2) and (2) adding a thickening agent into the mixed solution prepared in the step (1) for several times, and stirring to obtain the aqueous adhesive.
10. Use of the aqueous adhesive of any one of claims 1-8 in the preparation of shoes or bags.
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| CN107057627A (en) * | 2017-04-24 | 2017-08-18 | 丽水学院 | The preparation method of footwear environment-friendly type high performance water adhesive for polyurethane |
| CN108342180A (en) * | 2018-01-22 | 2018-07-31 | 运研材料科技（上海）有限公司 | A kind of aqueous viscose glue of water resistant low temperature and its application and the method for being bonded two layers of ox-hide product |
| CN110343499A (en) * | 2019-06-08 | 2019-10-18 | 东莞市罗孚化工有限公司 | A kind of aqueous adhesive and preparation method |
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| CN102618202A (en) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive |
| CN102838963A (en) * | 2012-09-13 | 2012-12-26 | 张明利 | Preparation method of high-temperature anti-yellowing polyurethane adhesive size |
| CN107057627A (en) * | 2017-04-24 | 2017-08-18 | 丽水学院 | The preparation method of footwear environment-friendly type high performance water adhesive for polyurethane |
| CN108342180A (en) * | 2018-01-22 | 2018-07-31 | 运研材料科技（上海）有限公司 | A kind of aqueous viscose glue of water resistant low temperature and its application and the method for being bonded two layers of ox-hide product |
| CN110343499A (en) * | 2019-06-08 | 2019-10-18 | 东莞市罗孚化工有限公司 | A kind of aqueous adhesive and preparation method |
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