CN111019557B - High-scratch-resistance leather adhesive - Google Patents
High-scratch-resistance leather adhesive Download PDFInfo
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- CN111019557B CN111019557B CN201911184326.3A CN201911184326A CN111019557B CN 111019557 B CN111019557 B CN 111019557B CN 201911184326 A CN201911184326 A CN 201911184326A CN 111019557 B CN111019557 B CN 111019557B
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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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
-
- 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
-
- 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
- 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
Abstract
The invention relates to the technical field of leather processing, and particularly discloses a high-scratch-resistance leather adhesive which comprises the following raw materials in parts by weight: 50-60 parts of gum arabic, 10-25 parts of sodium alginate, 10-15 parts of peach gum, 9-18 parts of modified phenolic resin, 3-7 parts of waste rubber micropowder, 1-3 parts of chitosan, 3-9 parts of cyanoacrylate, 0.2-0.9 part of a thickening agent, 0.1-0.8 part of a plasticizer, 0.3-0.5 part of a cross-linking agent, 0.5-1 part of a defoaming agent, 3-8 parts of a filler and 40-60 parts of deionized water, wherein the thickening agent is one of polyurethane resin or polymethacrylic resin, and the plasticizer is one of dibutyl phthalate, tricresyl phosphate and cyclohexane 1, 2-diisononyl phthalate. The invention overcomes the defects of the prior art, and the adhesive has the advantages of high viscosity, strong adhesiveness, good moldability, environmental protection and no irritation, and also has the advantage of outstanding scratch resistance.
Description
Technical Field
The invention relates to the technical field of leather processing, and particularly belongs to a high-scratch-resistance leather adhesive.
Background
With the development of technology, leather products have been produced in a variety of ways, and the lives of people are enriched. In the process of leather production, the bonding process of leather is an important process, and the leather bonding agent affects the quality of leather products.
The existing adhesive damages an adhesive film formed by the adhesive under the action of external force, such as scraping, rubbing, pulling and the like, and the adhesive film is hard, so that the overall crack and even breakage are easy to occur, and the service life of the adhesive is reduced; meanwhile, leather adhesives in the market generally have pungent smell, the leather adhesives are greatly damaged by long-time contact and breathing, and the environment is polluted by the discharged wastewater in the production process.
Disclosure of Invention
The invention aims to provide a leather adhesive with high scratch resistance, which overcomes the defects of the prior art, has the advantages of high viscosity, strong adhesiveness, good moldability, environmental protection and no irritation, and also has the outstanding advantage of scratch resistance.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the high-scratch-resistance leather adhesive comprises the following raw materials in parts by weight: 50-60 parts of gum arabic, 10-25 parts of sodium alginate, 10-15 parts of peach gum, 9-18 parts of modified phenolic resin, 3-7 parts of waste rubber micropowder, 1-3 parts of chitosan, 3-9 parts of cyanoacrylate, 0.2-0.9 part of thickening agent, 0.1-0.8 part of plasticizer, 0.3-0.5 part of cross-linking agent, 0.5-1 part of defoaming agent, 3-8 parts of filler and 40-60 parts of deionized water, wherein the thickening agent is one of polyurethane resin or polymethacrylic resin, and the plasticizer is one of dibutyl phthalate, tricresyl phosphate and cyclohexane 1, 2-diisononyl phthalate;
the preparation method of the modified phenolic resin comprises the following steps:
(1) according to the molar ratio of phenol to formaldehyde of 1: 3, adding phenol and formaldehyde into the reaction vessel, and stirring the mixture according to the molar ratio of urea to formaldehyde of 1: 1.2, adding urea into the mixed reaction system, adding an alkaline pH regulator to regulate the pH to 7-8, and heating in a water bath to 70-90 ℃; then cooling the mixture to room temperature by cold water;
(2) when the reaction system is cooled to normal temperature, adding melamine and formaldehyde into the reaction system according to the molar ratio of 1: 2, slowly adding melamine and formaldehyde solution, and keeping the temperature at 45-60 ℃ to obtain the modified phenolic resin solution.
Further, the feed comprises the following raw materials in parts by weight: 55 parts of gum arabic, 17.5 parts of sodium alginate, 12.5 parts of peach gum, 13.5 parts of modified phenolic resin, 5 parts of waste rubber micropowder, 2 parts of chitosan, 6 parts of cyanoacrylate, 0.55 part of thickening agent, 0.45 part of plasticizer, 0.4 part of cross-linking agent, 0.75 part of defoaming agent, 5.5 parts of filler and 50 parts of deionized water.
Further, the cross-linking agent is ferrous sulfate.
Further, the defoaming agent is polydimethylsiloxane.
Further, the filler is one or combination of more of attapulgite clay, kaolin, wollastonite and active silica micropowder.
A preparation method of a leather adhesive with high scratch resistance is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing the components according to the weight ratio;
(2) sequentially adding gum arabic, sodium alginate, peach gum, modified phenolic resin, cyanoacrylate and half of deionized water into a reaction kettle, starting up and stirring, heating to 85-95 ℃, keeping the temperature, continuing stirring for 60-75min, and cooling to room temperature to obtain viscous colloid;
(3) and (3) adding the waste rubber micro powder, the chitosan, the thickening agent, the filler and the other half of deionized water into the reaction system in the step (2), heating to 70-80 ℃, continuing stirring for 30-45min, then sequentially adding the plasticizer, the cross-linking agent and the defoaming agent into the reaction kettle, stirring uniformly, keeping the temperature for 40min, and cooling to 25 ℃ to obtain the high scratch resistance leather adhesive.
Compared with the prior art, the invention has the following implementation effects:
according to the high-scratch-resistance leather adhesive disclosed by the invention, the modified phenolic resin is added into the adhesive, so that the toughness and the friction resistance of the adhesive are improved, and the strength and the scratch resistance of the adhesive are improved; the plasticizer and the thickening agent are reasonably selected, so that the viscosity of the adhesive is improved, and the adhesive has the advantage of soft performance; the adhesive is made of environment-friendly materials, so that the environmental pollution is reduced, the harm to a human body is avoided, and the adopted waste rubber micro powder is the resource utilization after the waste rubber is purified and crushed; the method is simple to operate, low in cost and suitable for industrial large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples, and any modification is within the scope of the present invention without departing from the spirit of the present invention.
Example 1
The embodiment provides a preparation method of a high scratch resistance leather adhesive, which comprises the following steps:
(1) weighing the following raw materials in parts by weight: 50kg of gum arabic, 10kg of sodium alginate, 10kg of peach gum, 9kg of modified phenolic resin, 3kg of waste rubber micro powder, 1kg of chitosan, 3kg of cyanoacrylate, 0.2kg of polyurethane resin, 0.1kg of cyclohexane 1, 2-diisononyl phthalate, 0.3kg of ferrous sulfate, 0.5kg of polydimethylsiloxane, 3kg of active silicon micro powder and 40kg of deionized water;
(2) sequentially adding gum arabic, sodium alginate, peach gum, modified phenolic resin, cyanoacrylate and 20kg of deionized water into a reaction kettle, starting up and stirring, heating to 85-95 ℃, keeping the temperature, continuing stirring for 60-75min, and cooling to room temperature to obtain viscous colloid;
(3) adding the waste rubber micro powder, the chitosan, the polyurethane resin, the active silicon micro powder and 20kg of deionized water into the reaction system in the step (2), heating to 70-80 ℃, continuing to stir for 30-45min, then sequentially adding cyclohexane 1, 2-diisononyl diformate, ferrous sulfate and polydimethylsiloxane into the reaction kettle, stirring uniformly, keeping the temperature for 40min, and then cooling to 25 ℃, thus obtaining the high scratch resistance leather adhesive.
The preparation method of the modified phenolic resin comprises the following steps:
(1) according to the molar ratio of phenol to formaldehyde of 1: 3, adding phenol and formaldehyde into the reaction vessel, and stirring the mixture according to the molar ratio of urea to formaldehyde of 1: 1.2, adding urea into the mixed reaction system, adding an alkaline pH regulator to regulate the pH to 7-8, and heating in a water bath to 70-90 ℃; then cooling the mixture to room temperature by cold water;
(2) when the reaction system is cooled to normal temperature, adding melamine and formaldehyde into the reaction system according to the molar ratio of 1: 2, slowly adding melamine and formaldehyde solution, and keeping the temperature at 45-60 ℃ to obtain the modified phenolic resin solution.
Example 2
The embodiment provides a preparation method of a high scratch resistance leather adhesive, which comprises the following steps:
(1) weighing the following raw materials in parts by weight: 55kg of gum arabic, 17.5kg of sodium alginate, 12.5kg of peach gum, 13.5kg of modified phenolic resin, 4.5kg of waste rubber micro powder, 2kg of chitosan, 6kg of cyanoacrylate, 0.55kg of polyurethane resin, 0.45kg of cyclohexane 1, 2-diisononyl phthalate, 0.4kg of ferrous sulfate, 0.75kg of polydimethylsiloxane, 5.5kg of active silicon micro powder and 50kg of deionized water;
(2) sequentially adding gum arabic, sodium alginate, peach gum, modified phenolic resin, cyanoacrylate and 25kg of deionized water into a reaction kettle, starting up and stirring, heating to 85-95 ℃, keeping the temperature, continuing stirring for 60-75min, and cooling to room temperature to obtain viscous colloid;
(3) adding waste rubber micro powder, chitosan, polyurethane resin, active silicon micro powder and 25kg of deionized water into the reaction system in the step (2), heating to 70-80 ℃, continuing to stir for 30-45min, then sequentially adding cyclohexane 1, 2-diisononyl diformate, ferrous sulfate and polydimethylsiloxane into the reaction kettle, stirring uniformly, keeping the temperature for 40min, and then cooling to 25 ℃, thus obtaining the high scratch resistance leather adhesive.
The preparation method of the modified phenolic resin comprises the following steps:
(1) according to the molar ratio of phenol to formaldehyde of 1: 3, adding phenol and formaldehyde into the reaction vessel, and stirring the mixture according to the molar ratio of urea to formaldehyde of 1: 1.2, adding urea into the mixed reaction system, adding an alkaline pH regulator to regulate the pH to 7-8, and heating in a water bath to 70-90 ℃; then cooling the mixture to room temperature by cold water;
(2) when the reaction system is cooled to normal temperature, adding melamine and formaldehyde into the reaction system according to the molar ratio of 1: 2, slowly adding melamine and formaldehyde solution, and keeping the temperature at 45-60 ℃ to obtain the modified phenolic resin solution.
Example 3
The embodiment provides a preparation method of a high scratch resistance leather adhesive, which comprises the following steps:
(1) weighing the following raw materials in parts by weight: 60kg of Arabic gum, 25kg of sodium alginate, 15kg of peach gum, 18kg of modified phenolic resin, 7kg of waste rubber micro powder, 3kg of chitosan, 9kg of cyanoacrylate, 0.9kg of polyurethane resin, 0.8kg of cyclohexane 1, 2-diisononyl phthalate, 0.5kg of ferrous sulfate, 1kg of polydimethylsiloxane, 8kg of active silicon micro powder and 60kg of deionized water;
(2) sequentially adding gum arabic, sodium alginate, peach gum, modified phenolic resin, cyanoacrylate and 30kg of deionized water into a reaction kettle, starting up and stirring, heating to 85-95 ℃, keeping the temperature, continuing stirring for 60-75min, and cooling to room temperature to obtain viscous colloid;
(3) adding waste rubber micro powder, chitosan, polyurethane resin, active silicon micro powder and 30kg of deionized water into the reaction system in the step (2), heating to 70-80 ℃, continuing to stir for 30-45min, then sequentially adding cyclohexane 1, 2-diisononyl diformate, ferrous sulfate and polydimethylsiloxane into the reaction kettle, stirring uniformly, keeping the temperature for 40min, and then cooling to 25 ℃ to obtain the high scratch resistance leather adhesive.
The preparation method of the modified phenolic resin comprises the following steps:
(1) according to the molar ratio of phenol to formaldehyde of 1: 3, adding phenol and formaldehyde into the reaction vessel, and stirring the mixture according to the molar ratio of urea to formaldehyde of 1: 1.2, adding urea into the mixed reaction system, adding an alkaline pH regulator to regulate the pH to 7-8, and heating in a water bath to 70-90 ℃; then cooling the mixture to room temperature by cold water;
(2) when the reaction system is cooled to normal temperature, adding melamine and formaldehyde into the reaction system according to the molar ratio of 1: 2, slowly adding melamine and formaldehyde solution, and keeping the temperature at 45-60 ℃ to obtain the modified phenolic resin solution.
Example 4
The procedure was substantially the same as the starting material and the preparation method of example 3 except that the thickener was replaced with a polymethacrylic resin.
Example 5
The procedure was essentially the same as the starting material and preparation of example 3, except that the plasticizer was replaced with dibutyl phthalate.
Example 6
The procedure was substantially the same as the starting material and preparation method of example 3 except that the plasticizer was replaced with tricresyl phosphate.
And (3) detection test:
seven groups of perfect leather were cut in the weft direction, and then surface layer adhesion was performed using the adhesives produced by the above preparation methods, and the properties thereof were measured, and the results are shown in table 1:
table 1: adhesive performance detection statistical table
According to the results in table 1, the preparation method provided by the invention has outstanding performance advantages in various performances compared with the prior art, and meets the market demand.
And (3) testing the scratch resistance:
the adhesives produced in examples 1 to 6 and the adhesives currently on the market were processed into seven test pieces having an outer diameter of 108mm and an inner diameter of 8mm, respectively. Taber grinding wheel: h-22. Weight of weight: 1000g (dead weight 250g +750g weight). Rotation speed: 72 RPM.
And (4) judging a result: the exposed substrate is unqualified.
The test results are shown in table 2:
table 2: statistics of scratch resistance test results
According to the statistical results in table 2, the adhesive produced by the preparation method provided by the invention has the advantage of high scratch resistance compared with the prior art.
The foregoing is merely exemplary and illustrative of the present inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the specific embodiments described by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims as defined in the accompanying claims.
Claims (5)
1. A leather adhesive with high scratch resistance, which is characterized in that: the composite material comprises the following raw materials in parts by weight:
50-60 parts of gum arabic, 10-25 parts of sodium alginate, 10-15 parts of peach gum and modified phenolic resin
9-18 parts of waste rubber micro powder, 3-7 parts of waste rubber micro powder, 1-3 parts of chitosan, 3-9 parts of cyanoacrylate and a thickening agent
0.2-0.9 part of plasticizer, 0.1-0.8 part of cross-linking agent, 0.3-0.5 part of defoaming agent and filler
3-8 parts of a material and 40-60 parts of deionized water, wherein the thickening agent is polyurethane resin or polymethacrylic acid
One of acid resin, the plasticizer is dibutyl phthalate, tricresyl phosphate, and cyclohexane
One of the alkane 1, 2-dicarboxylic acid diisononyl ester, wherein the cross-linking agent is ferrous sulfate;
the preparation method of the modified phenolic resin comprises the following steps:
(1) according to the molar ratio of phenol to formaldehyde of 1: 3 ratio of phenol to the reaction vessel
And formaldehyde, wherein the molar ratio of urea to formaldehyde in stirring is 1: 1.2 proportional to Mixed reaction System
Adding urea, adding an alkaline pH regulator to regulate the pH to 7-8, and heating in a water bath to 70-90 ℃;
then cooling the mixture to room temperature by cold water;
(2) when the reaction system is cooled to normal temperature, adding melamine and formaldehyde into the reaction system according to the mol ratio
The molar ratio is 1: 2, slowly adding melamine and formaldehyde solution at the temperature of 45-60 DEG C
And (4) warming to obtain a modified phenolic resin solution.
2. The high scratch resistance leather adhesive according to claim 1, wherein: comprises that
The following raw materials in parts by weight: 55 parts of Arabic gum, 17.5 parts of sodium alginate, 12.5 parts of peach gum,
13.5 parts of modified phenolic resin, 5 parts of waste rubber micro powder, 2 parts of chitosan, 6 parts of cyanoacrylate, 2 parts of acrylic acid, and,
0.55 part of thickening agent, 0.45 part of plasticizer, 0.4 part of cross-linking agent, 0.75 part of defoaming agent and 5.5 parts of filler
Parts and 50 parts of deionized water.
3. The high scratch resistance leather adhesive according to claim 1, wherein: the above-mentioned
The defoaming agent is polydimethylsiloxane.
4. The high scratch resistance leather adhesive according to claim 1, wherein: the above-mentioned
The filler is one or more of attapulgite clay, kaolin, wollastonite and active silicon micro powder
And (6) mixing.
5. The method for preparing the leather adhesive with high scratch resistance according to claim 1, wherein the adhesive is prepared by mixing the raw materials
The method comprises the following steps: the method comprises the following steps:
(1) weighing the components according to the weight ratio;
(2) sequentially adding gum arabic, sodium alginate, peach gum and modified phenolic aldehyde tree into a reaction kettle
Starting up the machine to stir the grease, the cyanoacrylate and half of the deionized water, raising the temperature to 85-95 ℃, keeping the temperature and continuing to keep the temperature
Stirring for 60-75min, and cooling to room temperature to obtain viscous colloid;
(3) adding waste rubber micro powder, chitosan, a thickening agent into the reaction system in the step (2),
Heating the filler and the other half of deionized water to 70-80 deg.C, stirring for 30-45min, and adding water
Sequentially adding a plasticizer, a cross-linking agent and a defoaming agent into the reaction kettle, uniformly stirring, and keeping the temperature for 40min
And cooling to 25 ℃ to obtain the leather adhesive with high scratch resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911184326.3A CN111019557B (en) | 2019-11-27 | 2019-11-27 | High-scratch-resistance leather adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911184326.3A CN111019557B (en) | 2019-11-27 | 2019-11-27 | High-scratch-resistance leather adhesive |
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| Publication Number | Publication Date |
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| CN111019557A CN111019557A (en) | 2020-04-17 |
| CN111019557B true CN111019557B (en) | 2021-07-13 |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007281272B2 (en) * | 2006-07-31 | 2012-09-13 | Lubrizol Advanced Materials, Inc. | Aqueous dispersions of polyurethane compositions with ketone-hydrazide |
| CN100516104C (en) * | 2006-12-15 | 2009-07-22 | 浙江林学院 | Melamine and urea modified phenolic resin and its production process |
| CN101205449B (en) * | 2007-12-05 | 2012-02-22 | 东莞市英科水墨有限公司 | Leather binder and preparation thereof |
| CN104479617B (en) * | 2014-12-17 | 2018-06-12 | 广东菲安妮皮具股份有限公司 | High resistance to scraping leather adhesive |
| CN104497950B (en) * | 2014-12-17 | 2017-11-28 | 广东菲安妮皮具股份有限公司 | Leather adhesive and preparation method thereof |
| CN107057604B (en) * | 2017-06-06 | 2018-12-04 | 合肥雅克丽新型建材有限公司 | A kind of water pipe adhesive and preparation method thereof |
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Denomination of invention: A kind of leather adhesive with high scratch resistance Effective date of registration: 20221124 Granted publication date: 20210713 Pledgee: Yuexi Anhui rural commercial bank Limited by Share Ltd. Pledgor: YUEXI COUNTY TIANEN LEATHER GOODS CO.,LTD. Registration number: Y2022980023357 |
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