CN111269682A - Water-based adhesive for spraying and preparation method and application thereof - Google Patents
Water-based adhesive for spraying and preparation method and application thereof Download PDFInfo
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- CN111269682A CN111269682A CN202010283461.XA CN202010283461A CN111269682A CN 111269682 A CN111269682 A CN 111269682A CN 202010283461 A CN202010283461 A CN 202010283461A CN 111269682 A CN111269682 A CN 111269682A
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- parts
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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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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
- A43D25/00—Devices for gluing shoe parts
- A43D25/047—Devices for lasting with adhesives or for gluing together insoles and uppers
Abstract
The invention discloses a water-based adhesive for spraying, which comprises the following components in parts by weight: 65-100 parts of aqueous polyurethane emulsion, 1-10 parts of film-forming additive, 0.2-2 parts of defoaming agent, 0.2-2 parts of wetting agent and 0.1-2 parts of thickening agent. The water-based adhesive for spraying is used by matching with automatic spraying equipment in the shoe industry, and can realize continuous spraying in the shoe making process; the atomization effect is good, and the nozzle and the pipeline cannot be blocked in the spraying process; the glue layer has good heat resistance and high bonding strength, simultaneously has hydrolysis resistance, and can meet the related performance requirements of finished shoes; the automatic spraying process of the water-based adhesive for spraying is quicker than the painting process, and can replace manual painting in the traditional process flow, reduce assembly line operators and reduce the using amount of the adhesive, thereby reducing the production cost. Meanwhile, the invention also discloses a preparation method and application of the water-based adhesive for spraying.
Description
Technical Field
The invention relates to the field of aqueous adhesives, in particular to an aqueous adhesive for spraying and a preparation method and application thereof.
Background
In the traditional shoe making process, glue is manually coated, and 4 glue brushing workers are usually required for one production line. In order to reduce the manpower requirement of the shoe industry and improve the shoe manufacturing efficiency, automatic continuous production is always the aim of pursuing by the shoe industry, wherein the most important link is to realize automatic spraying of glue. Continuous mass production of sprayed oily glue is realized in the industry at present, but the oily glue contains higher VOC and is not beneficial to environmental protection and the health of field personnel, and the aqueous glue can well solve the problems.
The pipeline and the nozzle are easily blocked in the common water-based adhesive spraying process; in addition, in order to obtain better hydrolysis resistance, the aqueous adhesive needs to be added with a hardening agent, so that the aqueous adhesive is easier to block pipelines and nozzles, and is not beneficial to cleaning equipment.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the automatic spraying water-based adhesive. The spraying aqueous adhesive has good atomization effect, and the nozzle and the pipeline are not easy to block in the spraying process; the composite material also has other conventional mechanical properties such as better hydrolysis resistance and the like on the premise of not adding a hardening agent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the water-based adhesive for spraying comprises the following components in parts by weight: 65-100 parts of aqueous polyurethane emulsion, 1-10 parts of film-forming additive, 0.2-2 parts of defoaming agent, 0.2-2 parts of wetting agent and 0.1-2 parts of thickening agent.
The aqueous adhesive for spraying disclosed by the invention uses polyurethane as a main base material, so that the atomization effect is good, and the nozzle and the pipeline cannot be blocked in the spraying process; the glue layer has good heat resistance and high bonding strength, simultaneously has hydrolysis resistance, and can meet the related performance requirements of finished shoes. The automatic spraying process of the water-based adhesive for spraying is quicker than the painting process, can replace manual painting in the traditional process flow, can reduce assembly line operators, and can reduce the using amount of the adhesive, thereby reducing the production cost.
Preferably, the water-based adhesive for spraying comprises the following components in parts by weight: 85-95 parts of aqueous polyurethane emulsion, 1-5 parts of film-forming additive, 0.2-1.5 parts of defoaming agent, 0.2-1.5 parts of wetting agent and 0.1-2 parts of thickening agent.
Preferably, the aqueous polyurethane emulsion is a mixture of polyether polyol polyurethane and polyester polyol polyurethane.
More preferably, the aqueous polyurethane emulsion comprises the following components in parts by weight: 0-20 parts of polyether polyol polyurethane and 80-100 parts of polyester polyol polyurethane.
The aqueous polyurethane emulsion has high bonding strength, good heat resistance, good initial adhesion and hydrolysis resistance, and the prepared glue can be suitable for various shoe types, especially for outdoor shoe types and sports shoes with water resistance requirements.
Preferably, the average particle size of the aqueous polyurethane emulsion is less than 0.2 microns. The aqueous polyurethane emulsion has good hydrolysis resistance, and meanwhile, the emulsion has good stability, is also beneficial to spraying, is not easy to block pipelines and nozzles, and is also beneficial to improving the atomization effect.
More preferably, the polyurethane emulsion is a Covestro (formerly Bayer) product of the U58 series.
Preferably, the film forming aid is an alcohol ester compound. The film forming additive effectively reduces the lowest film forming temperature of the glue, is beneficial to the film forming performance of the glue, has good hydrolytic stability and has little influence on the hydrolytic resistance of the glue.
Preferably, the defoaming agent is at least one of polyether defoaming agent, silicone defoaming agent and polyether modified silicone defoaming agent. The defoaming agent has good defoaming effect and small influence on the viscosity of glue; can be but is not limited to BYK organosilicon series and air chemistry polyether siloxy series defoaming agent products.
Preferably, the wetting agent is at least one of alkyl sulfate wetting agents, polyoxyethylene alkylphenol ether wetting agents and silanol wetting agents. The wetting agent can enable the glue to be better spread on the surface of the material, so that the glue film is uniform and has no shrinkage phenomenon; can be but is not limited to polyether modified siloxane wetting agent (BYK series), acetylene glycol nonionic surfactant (air chemical series) products.
Preferably, the thickening agent is at least one of cellulose thickening agent, polyacrylic acid thickening agent and nonionic polyurethane thickening agent; can be but is not limited to Van chemical non-ionic polyurethane thickening agent series products.
Meanwhile, the invention also provides a preparation method of the water-based adhesive for spraying, which comprises the following steps:
(1) adding the aqueous polyurethane emulsion and the film-forming assistant according to the proportion, and stirring for 10-20 minutes;
(2) adding a wetting agent, and stirring for 10-20 minutes;
(3) adding a defoaming agent, and stirring for 10-20 minutes;
(4) adding a thickening agent to adjust the viscosity to the required viscosity, and filtering the obtained mixture to obtain the water-based adhesive for spraying.
The invention also provides application of the water-based adhesive for spraying in preparation of shoe materials. The spraying water-based adhesive used in the invention utilizes automatic equipment to spray and seal the treated sole, and can be activated in an oven at 55-65 ℃ within 72 hours for 2-3 minutes, and then is attached, pressed and cooled with the vamp which is glued, dried and activated, so that the finished shoe is manufactured.
Compared with the prior art, the invention has the beneficial effects that:
the water-based adhesive for spraying has good atomization effect, is not easy to block a nozzle and a pipeline in the spraying process, is suitable for automatic spraying equipment, and can realize continuous spraying in a shoemaking process; the thickness of the sprayed glue film is more uniform than that of the traditional coating process, the spraying process is easier to control, glue accumulation is not easy to generate, and the spraying process is easier to dry.
The water-based adhesive for spraying has high bonding strength, good heat resistance, good initial adhesion and hydrolysis resistance, and can be applied to various shoe types, particularly outdoor shoe types and sports shoes with water resistance requirements.
The spraying aqueous adhesive can reduce the using amount of the adhesive, 4 adhesive brushing workers can be reduced by one production line, and the labor cost is reduced; meanwhile, automation is also beneficial to improving the production efficiency; in addition, the water-based adhesive does not contain VOC, is more environment-friendly and is beneficial to the health of workers.
Drawings
FIG. 1 is a flow chart of a method for preparing the aqueous coating composition of the present invention;
FIG. 2 is a flow chart of the method of applying the aqueous gel for spraying of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
The spraying water-based adhesive comprises the following components in parts by weight: the coating comprises a mixture of polyether polyol polyurethane and polyester polyol polyurethane (U58: 90 parts), a film-forming aid (dodecyl alcohol ester) 5 parts, a polyether modified silicone defoamer (BYK 024: 0.2 part, 902W: 0.2 part), a silanol wetting agent (BYK 349: 0.2 part, 104 BC: 0.3 part), and a nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part, U300: 0.1 part).
The aqueous glue for spraying described in this example was prepared by the following method, as shown in fig. 1:
(1) adding the specific aqueous polyurethane emulsion and the film-forming assistant in sequence according to the proportion, and stirring for 10-20 minutes;
(2) adding a wetting agent, and stirring for 10-20 minutes;
(3) adding a defoaming agent, and stirring for 10-20 minutes;
(4) adding a thickening agent to adjust the viscosity to be required (1000-3000 cps), and filtering the obtained mixture by using a two-hundred-mesh filter screen to obtain the water-based adhesive for spraying.
Example 2
The spraying water-based adhesive comprises the following components in parts by weight:
the coating comprises a mixture of polyether polyol polyurethane and polyester polyol polyurethane (U58: 85 parts), 1 part of a film-forming aid (dodecyl alcohol ester), 0.1 part of a polyether modified silicone defoaming agent (BYK 024: 0.1 part, 902W: 0.1 part), 0.1 part of a silanol wetting agent (BYK 349: 0.1 part, 104 BC: 0.1 part) and a nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part and U300: 0.1 part).
The preparation method of the water-based adhesive for spraying in this example is the same as that of example 1.
Example 3
The spraying water-based adhesive comprises the following components in parts by weight:
the coating comprises a mixture of polyether polyol polyurethane and polyester polyol polyurethane (U58: 95 parts), a film-forming aid (dodecyl alcohol ester) 5 parts, a polyether modified silicone defoamer (BYK 024: 0.2 part, 902W: 0.3 part), a silanol wetting agent (BYK 349: 0.3 part, 104 BC: 0.4 part), and a nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part, U300: 0.1 part).
The preparation method of the water-based adhesive for spraying in this example is the same as that of example 1.
Example 4
The spraying water-based adhesive comprises the following components in parts by weight: the coating comprises a mixture of polyether polyol polyurethane and polyester polyol polyurethane (U58: 100 parts), a film-forming aid (dodecyl alcohol ester) 10 parts, a polyether modified silicone defoaming agent (BYK 024: 1 part, 902W: 1 part), a silanol wetting agent (BYK 349: 1 part, 104 BC: 1 part) and a nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part and U300: 0.1 part).
The preparation method of the water-based adhesive for spraying in this example is the same as that of example 1.
Example 5
The spraying water-based adhesive comprises the following components in parts by weight: the coating comprises a mixture of polyether polyol polyurethane and polyester polyol polyurethane (U58: 65 parts), 1 part of a film-forming aid (dodecyl alcohol ester), 0.1 part of a polyether modified silicone defoaming agent (BYK 024: 0.1 part, 902W: 0.1 part), 0.1 part of a silanol wetting agent (BYK 349: 0.1 part, 104 BC: 0.1 part) and a nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part and U300: 0.1 part).
The preparation method of the water-based adhesive for spraying in this example is the same as that of example 1.
Example 6
The spraying water-based adhesive comprises the following components in parts by weight: common water-based polyurethane (U53: 90 parts), polyether modified organosilicon defoamer (BYK 024: 0.2 part and 902W: 0.2 part), silanol wetting agent (BYK 349: 0.2 part and 104 BC: 0.3 part) and nonionic polyurethane thickener (U902: 0.1 part, U604: 0.1 part and U300: 0.1 part).
The preparation method of the water-based adhesive for spraying in this example is the same as that of example 1.
The specific application method of the water-based adhesive for spraying is shown in the attached figure 2.
Spraying the treating agent on the sole bonding part under certain pressure by automatic spraying equipment, and drying at 50-55 deg.C for 1-2 min; after the treating agent is dried, spraying water-based adhesive for spraying on a joint part by using another automatic spraying device through a spray head, and then drying for 2-3min at 55-65 ℃ to ensure that the adhesive layer generates initial viscosity, so that the adhesive layer is jointed and pressed with the glued vamp which is treated by traditional coating, and the vamp and the adhesive layer on the sole are bonded.
Standing at room temperature for 5min, testing initial tension, standing for 24 hr, and testing later tension with standard of 3.0 kg/cm; and the glue in the traditional manual painting mode is used as a control group, and the specific test results are shown in tables 1, 2 and 3:
TABLE 1 adhesion Properties of materials prepared from examples 1-3 and control waterborne adhesives
As is apparent from Table 1, the late stage adhesive property of the shoe material manufactured by the water-based adhesive for spraying is close to the adhesive property of the glue coated by the traditional manual shoe material; at present, in the shoe glue industry, a shoe factory uses traditional water-based glue to spray 5-10 shoes at most, and a spray head needs to be cleaned once; the water-based adhesive for spraying is used for spraying in a factory, and can continuously spray 50 shoes without pipe blockage or nozzle blockage, so that the manufacturing efficiency of the factory is greatly improved.
TABLE 2 Heat resistance of materials prepared from examples 1-3 and the comparative water-based adhesives
As can be seen from Table 2, the heat resistance of the shoe material manufactured by the water-based adhesive for spraying of the invention in the early and later stages is close to the adhesion performance of the conventional manual shoe material coating adhesive.
Table 3 hydrolysis resistance of materials prepared from examples 1-3 and the comparative water-based adhesives
As can be seen from Table 3, according to the comparison of the data of the examples 1 and 6, the shoe material manufactured by the spraying water-based adhesive made of the special water-based polyurethane of the invention without adding a hardening agent has better hydrolysis resistance than the water-based adhesive made of the common water-based polyurethane by the same formula, and is also obviously better than the traditional single-component water-based adhesive; the hydrolysis resistance of the double-component water-based adhesive currently used in the shoe industry (brushing and non-automatic spraying) is similar to that of the double-component water-based adhesive.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The water-based adhesive for spraying is characterized by comprising the following components in parts by weight: 65-100 parts of aqueous polyurethane emulsion, 1-10 parts of film-forming additive, 0.2-2 parts of defoaming agent, 0.2-2 parts of wetting agent and 0.1-2 parts of thickening agent.
2. The aqueous adhesive for spraying according to claim 1, which comprises the following components in parts by weight: 85-95 parts of aqueous polyurethane emulsion, 1-5 parts of film-forming additive, 0.2-1.5 parts of defoaming agent, 0.2-1.5 parts of wetting agent and 0.1-2 parts of thickening agent.
3. The aqueous coating paste according to claim 1 or 2, wherein the aqueous polyurethane emulsion is a mixture of polyether polyol-based polyurethane and polyester polyol-based polyurethane.
4. The aqueous spray coating adhesive of claim 1 or 2, wherein the average particle size of the aqueous polyurethane emulsion is less than 0.2 μm.
5. The aqueous adhesive for spraying according to claim 1 or 2, wherein the film-forming aid is an alcohol ester compound.
6. The aqueous coating composition according to claim 1 or 2, wherein the defoaming agent is at least one of a polyether defoaming agent, a silicone defoaming agent and a polyether-modified silicone defoaming agent.
7. The aqueous paste for spraying according to claim 1 or 2, wherein the wetting agent is at least one of an alkylsulfate-based wetting agent, a polyoxyethylene alkylphenol ether-based wetting agent, and a silanol-based wetting agent.
8. The aqueous spray coating adhesive according to claim 1 or 2, wherein the thickener is at least one of a cellulose-based thickener, a polyacrylic-based thickener, and a nonionic polyurethane-based thickener.
9. A method for preparing the water-based adhesive for spraying according to any one of claims 1 to 8, which comprises the following steps:
(1) adding the aqueous polyurethane emulsion and the film-forming assistant according to the proportion, and stirring for 10-20 minutes;
(2) adding a wetting agent, and stirring for 10-20 minutes;
(3) adding a defoaming agent, and stirring for 10-20 minutes;
(4) adding a thickening agent to adjust the viscosity to the required viscosity, and filtering the obtained mixture to obtain the water-based adhesive for spraying.
10. Use of the aqueous spray coating according to any one of claims 1 to 8 for the production of shoe materials.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010283461.XA CN111269682A (en) | 2020-04-10 | 2020-04-10 | Water-based adhesive for spraying and preparation method and application thereof |
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| CN202010283461.XA CN111269682A (en) | 2020-04-10 | 2020-04-10 | Water-based adhesive for spraying and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861918A (en) * | 2021-10-12 | 2021-12-31 | 广东远东高分子科技有限公司 | Waterborne polyurethane adhesive for automatic spraying and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110178203A1 (en) * | 2009-10-19 | 2011-07-21 | Elmer's Products, Inc. | High strength glue formulation |
| CN102253502A (en) * | 2011-04-18 | 2011-11-23 | 广州奥翼电子科技有限公司 | Bonding agent and electro-optic assembly and electrophoretic medium thereof |
| CN106118577A (en) * | 2016-07-04 | 2016-11-16 | 黄淳 | A kind of footwear Bicompenent high solid content polyurethane adhesive and preparation method thereof |
| CN108239457A (en) * | 2016-12-23 | 2018-07-03 | 张家港康得新光电材料有限公司 | Aqueous peelable glue, preparation method and application |
| CN109266289A (en) * | 2018-08-29 | 2019-01-25 | 嘉善欣达胶业有限公司 | A kind of flock glue and preparation method thereof |
| CN109868091A (en) * | 2017-12-01 | 2019-06-11 | 万华化学（宁波）有限公司 | A kind of water vacuum plastics-absorption glue and preparation method thereof |
-
2020
- 2020-04-10 CN CN202010283461.XA patent/CN111269682A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110178203A1 (en) * | 2009-10-19 | 2011-07-21 | Elmer's Products, Inc. | High strength glue formulation |
| CN102253502A (en) * | 2011-04-18 | 2011-11-23 | 广州奥翼电子科技有限公司 | Bonding agent and electro-optic assembly and electrophoretic medium thereof |
| CN106118577A (en) * | 2016-07-04 | 2016-11-16 | 黄淳 | A kind of footwear Bicompenent high solid content polyurethane adhesive and preparation method thereof |
| CN108239457A (en) * | 2016-12-23 | 2018-07-03 | 张家港康得新光电材料有限公司 | Aqueous peelable glue, preparation method and application |
| CN109868091A (en) * | 2017-12-01 | 2019-06-11 | 万华化学（宁波）有限公司 | A kind of water vacuum plastics-absorption glue and preparation method thereof |
| CN109266289A (en) * | 2018-08-29 | 2019-01-25 | 嘉善欣达胶业有限公司 | A kind of flock glue and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李绍雄等: "《聚氨酯树脂及其应用》", 31 May 2002, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861918A (en) * | 2021-10-12 | 2021-12-31 | 广东远东高分子科技有限公司 | Waterborne polyurethane adhesive for automatic spraying and preparation method thereof |
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