CN111423823A - Water-based treating agent for vulcanized shoes and preparation method thereof - Google Patents
Water-based treating agent for vulcanized shoes and preparation method thereof Download PDFInfo
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- CN111423823A CN111423823A CN202010190291.0A CN202010190291A CN111423823A CN 111423823 A CN111423823 A CN 111423823A CN 202010190291 A CN202010190291 A CN 202010190291A CN 111423823 A CN111423823 A CN 111423823A
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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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
Abstract
The invention provides a water-based treating agent for vulcanized shoes and a preparation method thereof, wherein the water-based treating agent comprises the following raw materials in parts by weight: 50-70 parts of aqueous polyurethane dispersoid, 10-16 parts of methyl methacrylate, 12-15 parts of polyacrylate, 3.5-6 parts of nickel naphthenate, 2-8 parts of chlorinated polypropylene, 1.6-2.2 parts of toluene, 5-9 parts of diisocyanate, 16-19 parts of SBS graft, 3-4 parts of ethylene glycol monoethyl ether, 6-10 parts of nano silicon dioxide and 1-3 parts of ethyl acetate. The water-based treating agent for vulcanized shoes, which is prepared by the invention, has good heat resistance and high peel strength.
Description
Technical Field
The invention relates to the technical field of vulcanized shoe treating agents, and particularly relates to a water-based treating agent for vulcanized shoes and a preparation method thereof.
Background
The surface state of the shoe material is various and varies widely, and the polarity and chemical state of the surface are different from each other except for the presence of various attachments, and the shoe treating agent plays an extremely important role. If the surface of the adhesion surface is not modified by the treating agent, it is difficult to achieve a desired adhesion effect. The bonded material for shoes can effectively remove the physically adhered 'pollutant' on the surface if it can be treated with a treating agent before brushing glue, and more importantly, a new surface can be formed by attaching a layer of treating agent molecular film on the surface of the material, and the bonding agent can have good 'wetting' and 'affinity' effects on the new surface. That is, the treating agent can play a role of bridging between the surface of the material and the adhesive, so that the 'bondability' of the surface of the material is enhanced, and the wear resistance of the shoe is improved. In the vulcanized shoe manufacturing industry at present, a treating agent for producing vulcanized shoes is mainly a solvent-based treating agent, and a large amount of solvent products are used as the solvent-based treating agent, so that the environment is polluted, resources are wasted, and the physical health of workers in a shoe factory is influenced; the aqueous treatment agent is environment-friendly and saves resources.
Chinese patent CN102161868B reports a water-based treating agent for vulcanized shoes and a preparation method thereof, the water-based treating agent for vulcanized shoes is specially used for treating vamp materials for vulcanized shoes and comprises the following components in parts by weight: 80-120 parts of aqueous polyurethane dispersion, 0.1-0.5 part of cosolvent, 0.1-0.5 part of hydrolysis resistance agent, 0.2-0.5 part of defoaming agent, 3-10 parts of adhesion promoter and 0.2-0.5 part of thickening agent. However, the water-based treating agent prepared by the invention is easy to be debonded when the water-based treating agent is coated on the upper and passes through an oven.
In view of the above, it is an urgent need for those skilled in the art to develop an aqueous treating agent for vulcanized shoes which has good heat resistance and is not easily peeled off.
Disclosure of Invention
The invention aims to provide a water-based treating agent for vulcanized shoes and a preparation method thereof, which solve the problems of poor heat resistance, easy peeling and the like of the water-based treating agent for vulcanized shoes.
In order to solve the above problems, the present invention provides the following technical solutions: a water-based treating agent for vulcanized shoes and a preparation method thereof are as follows:
the water-based treating agent for vulcanized shoes is prepared from the following raw materials in parts by weight: 50-70 parts of aqueous polyurethane dispersoid, 10-16 parts of methyl methacrylate, 12-15 parts of polyacrylate, 3.5-6 parts of nickel naphthenate, 2-8 parts of chlorinated polypropylene, 1.6-2.2 parts of toluene, 5-9 parts of diisocyanate, 16-19 parts of SBS graft, 3-4 parts of ethylene glycol monoethyl ether, 6-10 parts of nano silicon dioxide and 1-3 parts of ethyl acetate.
Furthermore, the molecular weight of the aqueous polyurethane dispersion is 10000-12000.
Furthermore, the particle size of the nano silicon dioxide is 30 nm-40 nm.
Further, the preparation method of the SBS graft comprises the following steps: adding styrene butadiene rubber, benzoyl peroxide, potassium methacrylate and acrylic acid into a reaction kettle, stirring for 2-4 h under the protection of nitrogen, heating in a water bath to 40-45 ℃, and keeping the temperature for 4-5 h to obtain the SBS graft.
Further, in the preparation process of the SBS graft, the volume ratio of the styrene-butadiene rubber, the benzoyl peroxide, the potassium methacrylate to the acrylic acid is 10: 0.6: 3: 1.
another object of the present invention is to provide a method for preparing the above aqueous treating agent for vulcanized shoes, comprising the steps of:
step S1, adding the nano silicon dioxide in parts by weight into water, stirring for 1-2 h, adding the aqueous polyurethane dispersion in parts by weight, and stirring for 5-10 min to obtain a material A;
the heat resistance of the treating agent is greatly improved by the high molecular weight polyurethane molecular chain and the nano silicon dioxide, namely, the adhesive force under the high-temperature condition is improved, the upper is not easy to be separated when passing through an oven, and a better bonding effect is realized on shoe materials with larger tension.
Step S2, mixing the methyl methacrylate, the polyacrylate, the chlorinated polypropylene and the diisocyanate in parts by weight at the temperature of 30-40 ℃ to obtain a material B;
and step S3, stirring the SBS graft in parts by weight, the material A obtained in the step S1 and the material B obtained in the step S2 for 5-10 min, increasing the temperature, adding the nickel naphthenate, the toluene, the ethyl acetate and the ethylene glycol monoethyl ether in parts by weight, and continuously stirring for 20-40 min to obtain the water-based treating agent for the vulcanized shoes.
Further, in step S1, the stirring speed is 60 to 80 revolutions per minute.
Still further, in step S1, the volume ratio of the nano-silica to the water is 1: 5 to 6.
Still further, in step S3, the stirring speed is 300 to 500 revolutions per minute.
Further, in step S3, the temperature is raised to 40 to 45 ℃.
According to the technical scheme, the invention has the following beneficial effects:
the waterborne polyurethane dispersoid in the waterborne treating agent for vulcanized shoes has large molecular weight and small particle size, is activated under the action of heat and is easier to permeate into shoe materials, so that vulcanized shoes are bonded more firmly, and a high molecular weight polyurethane molecular chain cooperates with nano silicon dioxide to form an inorganic-organic composite framework structure, so that the heat resistance of the waterborne treating agent is greatly improved, the waterborne polyurethane dispersoid is easier to brush, the waterborne polyurethane dispersoid is quicker to dry after being brushed, the peel strength is high, and the waterborne polyurethane dispersoid can be better applied to vulcanized shoe production.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
Water-based treating agent for vulcanized shoes
The water-based treating agent for vulcanized shoes is prepared from the following raw materials in parts by weight: 50g of aqueous polyurethane dispersion, 10g of methyl methacrylate, 12g of polyacrylate, 3.5g of nickel naphthenate, 2g of chlorinated polypropylene, 1.6g of toluene, 5g of diisocyanate, 16g of SBS graft, 3g of ethylene glycol monoethyl ether, 6g of nano silicon dioxide and 1g of ethyl acetate.
The molecular weight of the aqueous polyurethane dispersion is 10000.
The particle size of the nano silicon dioxide is 30 nm.
The preparation method of the SBS graft comprises the following steps: adding styrene butadiene rubber, benzoyl peroxide, potassium methacrylate and acrylic acid into a reaction kettle, stirring for 2 hours under the protection of nitrogen, heating in a water bath, raising the temperature to 40 ℃, and preserving the heat for 4 hours to obtain the SBS graft.
In the preparation process of the SBS graft, the volume ratio of the styrene butadiene rubber, the benzoyl peroxide, the potassium methacrylate to the acrylic acid is 10: 0.6: 3: 1.
the preparation method of the water-based treating agent for vulcanized shoes comprises the following steps:
step S1, adding the nano silicon dioxide in parts by weight into water, stirring for 1h, wherein the volume ratio of the nano silicon dioxide to the water is 1: 5, adding the aqueous polyurethane dispersion in parts by weight, and stirring for 5min at a stirring speed of 60 revolutions per minute to obtain a material A;
step S2, mixing the methyl methacrylate, the polyacrylate, the chlorinated polypropylene and the diisocyanate in parts by weight at the temperature of 30 ℃ to obtain a material B;
and step S3, stirring the SBS graft in parts by weight, the material A obtained in the step S1 and the material B obtained in the step S2 for 5min, increasing the temperature to 40 ℃, adding the nickel naphthenate, the toluene, the ethyl acetate and the ethylene glycol monoethyl ether in parts by weight, and continuously stirring for 20min at the stirring speed of 300 revolutions per minute to obtain the water-based treating agent for the vulcanized shoes.
Example 2
Water-based treating agent for vulcanized shoes
The water-based treating agent for vulcanized shoes is prepared from the following raw materials in parts by weight: 70g of aqueous polyurethane dispersion, 16g of methyl methacrylate, 15g of polyacrylate, 6g of nickel naphthenate, 8g of chlorinated polypropylene, 2.2g of toluene, 9g of diisocyanate, 19g of SBS graft, 4g of ethylene glycol monoethyl ether, 10g of nano silicon dioxide and 3g of ethyl acetate.
The molecular weight of the aqueous polyurethane dispersion was 12000.
The particle size of the nano silicon dioxide is 40 nm.
The preparation method of the SBS graft comprises the following steps: adding styrene butadiene rubber, benzoyl peroxide, potassium methacrylate and acrylic acid into a reaction kettle, stirring for 4 hours under the protection of nitrogen, heating in a water bath, raising the temperature to 45 ℃, and preserving the temperature for 5 hours to obtain the SBS graft.
In the preparation process of the SBS graft, the volume ratio of the styrene butadiene rubber, the benzoyl peroxide, the potassium methacrylate to the acrylic acid is 10: 0.6: 3: 1.
the preparation method of the water-based treating agent for vulcanized shoes comprises the following steps:
step S1, adding the nano silicon dioxide in parts by weight into water, stirring for 2 hours, wherein the volume ratio of the nano silicon dioxide to the water is 1: 6, adding the aqueous polyurethane dispersion in parts by weight, and stirring for 10min at a stirring speed of 80 rpm to obtain a material A;
step S2, mixing the methyl methacrylate, the polyacrylate, the chlorinated polypropylene and the diisocyanate in parts by weight at the temperature of 40 ℃ to obtain a material B;
and step S3, stirring the SBS graft in parts by weight, the material A obtained in the step S1 and the material B obtained in the step S2 for 10min, increasing the temperature to 45 ℃, adding the nickel naphthenate, the toluene, the ethyl acetate and the ethylene glycol monoethyl ether in parts by weight, and continuously stirring for 40min at the stirring speed of 500 revolutions per minute to obtain the water-based treating agent for the vulcanized shoes.
Example 3
Water-based treating agent for vulcanized shoes
The water-based treating agent for vulcanized shoes is prepared from the following raw materials in parts by weight: 60g of aqueous polyurethane dispersion, 14g of methyl methacrylate, 13g of polyacrylate, 4g of nickel naphthenate, 5g of chlorinated polypropylene, 2g of toluene, 7g of diisocyanate, 17g of SBS graft, 3.4g of ethylene glycol monoethyl ether, 9g of nano silicon dioxide and 2g of ethyl acetate.
The molecular weight of the aqueous polyurethane dispersion is 11000.
The particle size of the nano silicon dioxide is 35 nm.
The preparation method of the SBS graft comprises the following steps: adding styrene butadiene rubber, benzoyl peroxide, potassium methacrylate and acrylic acid into a reaction kettle, stirring for 3 hours under the protection of nitrogen, heating in a water bath, raising the temperature to 40 ℃, and preserving the temperature for 5 hours to obtain the SBS graft.
In the preparation process of the SBS graft, the volume ratio of the styrene butadiene rubber, the benzoyl peroxide, the potassium methacrylate to the acrylic acid is 10: 0.6: 3: 1.
the preparation method of the water-based treating agent for vulcanized shoes comprises the following steps:
step S1, adding the nano silicon dioxide in parts by weight into water, stirring for 2 hours, wherein the volume ratio of the nano silicon dioxide to the water is 1: 5, adding the aqueous polyurethane dispersion in parts by weight, and stirring for 6min at a stirring speed of 70 revolutions per minute to obtain a material A;
step S2, mixing the methyl methacrylate, the polyacrylate, the chlorinated polypropylene and the diisocyanate in parts by weight at the temperature of 36 ℃ to obtain a material B;
and step S3, stirring the SBS graft in parts by weight, the material A obtained in the step S1 and the material B obtained in the step S2 for 8min, increasing the temperature to 45 ℃, adding the nickel naphthenate, the toluene, the ethyl acetate and the ethylene glycol monoethyl ether in parts by weight, and continuously stirring for 30min at the stirring speed of 400 revolutions per minute to obtain the water-based treating agent for the vulcanized shoes.
Examples of the experiments
The water-based treatment agent for vulcanized shoes obtained by the preparation methods of examples 1 to 3 of the present invention was measured for heat resistance according to GB/T32368-2015, peel strength according to GB/T2791-1995, and compared with a commercially available treatment agent test value under the same conditions, the results were as follows:
TABLE 1 Performance of the aqueous treating agent for vulcanized shoes obtained in examples 1 to 3 of the present invention and a commercially available treating agent
| Performance of | Example 1 | Example 2 | Example 3 | Commercially available treating agent |
| Heat resistance cm | 1.2 | 1.0 | 1.1 | 1.5 |
| Peel strength N/mm | 5.7 | 5.8 | 5.5 | 4.9 |
As can be seen from Table 1 above, the water-based treatment agent for vulcanized shoes prepared by the present invention has good heat resistance and high peel strength, and has better comprehensive performance compared with the commercially available treatment agent.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The water-based treating agent for vulcanized shoes is characterized by comprising the following raw materials in parts by weight: 50-70 parts of aqueous polyurethane dispersoid, 10-16 parts of methyl methacrylate, 12-15 parts of polyacrylate, 3.5-6 parts of nickel naphthenate, 2-8 parts of chlorinated polypropylene, 1.6-2.2 parts of toluene, 5-9 parts of diisocyanate, 16-19 parts of SBS graft, 3-4 parts of ethylene glycol monoethyl ether, 6-10 parts of nano silicon dioxide and 1-3 parts of ethyl acetate.
2. The aqueous treating agent for vulcanized shoes as described in claim 1, wherein the molecular weight of said aqueous polyurethane dispersion is 10000 to 12000.
3. The aqueous treating agent for vulcanized shoes as set forth in claim 1, wherein the nano silica has a particle size of 30 to 40 nm.
4. The aqueous treating agent for vulcanized shoes according to claim 1, wherein the SBS graft is prepared by the following steps: adding styrene butadiene rubber, benzoyl peroxide, potassium methacrylate and acrylic acid into a reaction kettle, stirring for 2-4 h under the protection of nitrogen, heating in a water bath to 40-45 ℃, and keeping the temperature for 4-5 h to obtain the SBS graft.
5. The aqueous treating agent for vulcanized shoes as recited in claim 4, wherein in the preparation process of the SBS graft, the volume ratio of the styrene-butadiene rubber, the benzoyl peroxide, the potassium methacrylate and the acrylic acid is 10: 0.6: 3: 1.
6. a method for preparing the aqueous treating agent for vulcanized shoes according to any one of claims 1 to 5, which comprises the following steps:
step S1, adding the nano silicon dioxide in parts by weight into water, stirring for 1-2 h, adding the aqueous polyurethane dispersion in parts by weight, and stirring for 5-10 min to obtain a material A;
step S2, mixing the methyl methacrylate, the polyacrylate, the chlorinated polypropylene and the diisocyanate in parts by weight at the temperature of 30-40 ℃ to obtain a material B;
and step S3, stirring the SBS graft in parts by weight, the material A obtained in the step S1 and the material B obtained in the step S2 for 5-10 min, increasing the temperature, adding the nickel naphthenate, the toluene, the ethyl acetate and the ethylene glycol monoethyl ether in parts by weight, and continuously stirring for 20-40 min to obtain the water-based treating agent for the vulcanized shoes.
7. The method for preparing an aqueous treating agent for vulcanized shoes according to claim 6, wherein the stirring speed is 60 to 80 revolutions per minute in step S1.
8. The method for preparing the aqueous treating agent for vulcanized shoes as recited in claim 6, wherein in step S1, the volume ratio of the nano silica to water is 1: 5 to 6.
9. The method for preparing an aqueous treating agent for vulcanized shoes according to claim 6, wherein the stirring speed is 300 to 500 rpm in step S3.
10. The method for preparing an aqueous treating agent for vulcanized shoes according to claim 6, wherein the temperature after the temperature rise in step S3 is 40 ℃ to 45 ℃.
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| CN202010190291.0A CN111423823A (en) | 2020-03-18 | 2020-03-18 | Water-based treating agent for vulcanized shoes and preparation method thereof |
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| CN202010190291.0A CN111423823A (en) | 2020-03-18 | 2020-03-18 | Water-based treating agent for vulcanized shoes and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161868A (en) * | 2011-03-01 | 2011-08-24 | 中部树脂化工有限公司 | Water-based treatment agent for vulcanized shoes and preparation method thereof |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN105017993A (en) * | 2015-08-10 | 2015-11-04 | 万华化学（广东）有限公司 | Aqueous binder for vulcanized shoe and preparation method of aqueous binder |
| CN109868107A (en) * | 2017-12-01 | 2019-06-11 | 万华化学（宁波）有限公司 | A kind of adhesive and its preparation method and application |
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2020
- 2020-03-18 CN CN202010190291.0A patent/CN111423823A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161868A (en) * | 2011-03-01 | 2011-08-24 | 中部树脂化工有限公司 | Water-based treatment agent for vulcanized shoes and preparation method thereof |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN105017993A (en) * | 2015-08-10 | 2015-11-04 | 万华化学（广东）有限公司 | Aqueous binder for vulcanized shoe and preparation method of aqueous binder |
| CN109868107A (en) * | 2017-12-01 | 2019-06-11 | 万华化学（宁波）有限公司 | A kind of adhesive and its preparation method and application |
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Application publication date: 20200717 |