阅读说明：本技术 单面上胶制备粘合制品的方法 (Method for preparing adhesive product by single-side sizing ) 是由 魏松丽 张晨曦 张海龙 李洪超 金晨 朱英丹 赵东波 于 2019-03-29 设计创作，主要内容包括：本发明涉及单面上胶制备粘合制品的方法,该方法制备得到的粘合制品以及粘合制品在鞋类生产中的应用。该方法包括以下步骤：a.将一清洁剂施涂到一第一基材的至少一个表面,干燥施加有所述清洁剂的第一基材表面；b.将一粘合剂施涂到一第二基材的至少一个表面,干燥施加有所述粘合剂的第二基材表面；和使经步骤a处理的第一基材表面和经步骤b处理的第二基材表面接触,得到所述粘合制品；所述清洁剂包含极性有机溶剂和聚异氰酸酯；所述极性有机溶剂是沸点不高于135℃且异氰酸酯非反应性的；所述聚异氰酸酯的异氰酸酯基团重量占清洁剂重量的0.005重量％-6重量％。(The invention relates to a method for producing a bonded article by single-sided gluing, to the bonded article produced by this method and to the use of the bonded article in the production of footwear. The method comprises the following steps: a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied; b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; and contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article; the cleaning agent comprises a polar organic solvent and a polyisocyanate; the polar organic solvent has a boiling point of not higher than 135 ℃ and is non-reactive with isocyanate; the polyisocyanate has an isocyanate group weight of 0.005 to 6 wt% based on the weight of the detergent.)

1. A method for preparing a bonded article by single-sided sizing, comprising the steps of:

a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied;

b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; and

c. contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article;

wherein the cleaning agent comprises a polar organic solvent and a polyisocyanate; the polar organic solvent has a boiling point of not higher than 135 ℃ and is non-reactive with isocyanate; the polyisocyanates correspond to the general formula R (NCO)_nWherein R is one or more of the following: aliphatic hydrocarbon groups having 2 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 15 carbon atoms and araliphatic hydrocarbon groups having 8 to 15 carbon atoms, n is not less than 2; the polyisocyanate has an isocyanate group weight of 0.005 to 6 wt% based on the weight of the detergent.

2. A process according to claim 1, wherein the polyisocyanate has an isocyanate group weight of from 0.007% to 5.6%, preferably from 0.01% to 4.5%, further preferably from 0.01% to 0.5%, still further preferably from 0.02% to 0.2%, yet further preferably from 0.02% to 0.085%, most preferably from 0.04% to 0.085% by weight of the detergent.

3. The method of claim 1 or 2, wherein the polar organic solvent is one or more of acetone, methyl ethyl ketone, ethyl acetate, or butyl acetate, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of methyl ethyl ketone and propylene glycol diacetate, or a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate; further preferred are a mixture of methyl ethyl ketone and ethyl acetate, a mixture of methyl ethyl ketone and butyl acetate, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of acetone and butyl acetate, a mixture of ethyl acetate and butyl acetate and methyl ethyl ketone, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate, methyl ethyl ketone or butyl acetate, and most preferred is methyl ethyl ketone.

4. The process according to claim 1 or 2, wherein n of the general formula of the polyisocyanate is 2.5 to 5.5, most preferably 2.5 to 4.

5. The method of claim 1 or 2, wherein the polyisocyanate is one or more of: toluene diisocyanate trimer, prepolymers of toluene diisocyanate and diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, prepolymers of diphenylmethane diisocyanate and tris (p-isocyanatophenyl) thiophosphate, most preferably one or more of the following: prepolymers of toluene diisocyanate and diphenylmethane diisocyanate, and trimers of toluene diisocyanate.

6. The method of claim 1 or 2, wherein the first substrate is one or more of: polyurethane-based materials and polyvinyl chloride-based materials, most preferably polyurethane-based synthetic leather.

7. The method of claim 1 or 2, wherein the cleaning agent comprises methyl ethyl ketone and a polyisocyanate having an isocyanate functionality of 2.5 to 4, the polyisocyanate being one or more of: a prepolymer of toluene diisocyanate and diphenylmethane diisocyanate, and a trimer of toluene diisocyanate, the isocyanate groups of the polyisocyanate being from 0.04% to 0.085% by weight of the detergent.

8. The method of claim 1 or 2, wherein the second substrate is pretreated prior to application of the adhesive, comprising the steps of:

i. polishing or cleaning the second substrate; and

applying a primer to the second substrate treated in step i.

9. The method of claim 1 or 2, wherein prior to step c, the surface of the second substrate treated in step b to which the adhesive is applied is heat activated at a temperature of from 45 ℃ to 75 ℃.

10. An adhesive article made according to the method of any one of claims 1-9.

11. Use of an adhesive article according to claim 10 in the production of footwear.

Technical Field

The invention relates to a method for producing a bonded article by single-sided gluing, to the bonded article produced by this method and to the use of the bonded article in the production of footwear.

Background

The traditional process for bonding shoe materials in the shoe industry is a double-sided gluing process, i.e., the adhesive is applied to the upper of the sole or the outsole of the midsole, and often requires cleaning and priming of the midsole, outsole and upper prior to application of the adhesive. For example, CN1235966C discloses a laminate comprising a layer of foamed product and a layer of polyolefin material, the bonding of which is by double-sided gluing. However, because the shoe making industry faces the problems of high labor cost, complex gluing process and low production efficiency, the shoe making industry hopes to find a simplified shoe making process.

The single-side gluing process reduces the gluing step, saves labor force, improves production efficiency, and can avoid the vamp from being polluted by the adhesive, thereby being popular in the shoe making industry. The difficulty with single-sided sizing processes is the need to find suitable substrate treating agents and adhesives.

Hot melt adhesives, which can be applied in single-sided gluing processes, have limited application in the shoe-making industry due to their poor initial performance, high equipment costs, and the like. Attempts have also been made in the industry to use aqueous polyurethane dispersion adhesives for single-sided sizing processes.

CN1098154C discloses a process for injection molding for preparing a laminate by applying a primer comprising an organic solvent and an ethylene or propylene polymer onto which an unsaturated carboxylic acid or its anhydride, ester, amide, imide or metal salt is grafted to a substrate and injection molding the ethylene or propylene polymer onto the primed substrate. This method is not suitable for the application process.

CN107802056A discloses a method for manufacturing shoes by applying powder glue on single surface. The powder glue adopted by the method comprises common polyurethane resin and polyamide resin, and the mechanical property of the shoe material prepared by single-side gluing is far different from that of the shoe material prepared by double-side gluing.

Therefore, there is a need in the industry to develop a single-sided sizing process that provides products with good bond strength, heat resistance, and hydrolysis resistance.

Disclosure of Invention

The invention aims to provide a method for preparing a bonded product by single-sided sizing, the bonded product prepared by the method and application of the bonded product in the production of shoes.

The method for preparing the bonding product by single-sided sizing comprises the following steps:

a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied;

b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; and

c. contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article;

wherein the cleaning agent comprises a polar organic solvent and a polyisocyanate; the polar organic solvent has a boiling point of not higher than 135 ℃ and is non-reactive with isocyanate; the polyisocyanates correspond to the general formula R (NCO)_nWherein R is one or more of the following: aliphatic hydrocarbon groups having 2 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 15 carbon atoms and araliphatic hydrocarbon groups having 8 to 15 carbon atoms, n is not less than 2; the polyisocyanate has an isocyanate group weight of 0.005 to 6 wt% based on the weight of the detergent.

According to one aspect of the present invention, there is provided an adhesive article prepared according to the method provided herein.

According to a further aspect of the invention there is provided the use of an adhesive article provided according to the invention in the manufacture of footwear.

The bonded product obtained by the single-sided sizing method has good initial bonding strength, final bonding strength, heat resistance and hydrolysis resistance.

Drawings

The invention will be described and explained in more detail below with reference to the drawings, in which:

FIG. 1 is a schematic representation of sample adhesion.

FIG. 2 is a schematic diagram of a sample heat resistance or hydrolysis resistance test.

Detailed Description

The invention provides a method for preparing a bonding product by single-sided sizing, which comprises the following steps: a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied; b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article; wherein the polar organic solvent has a boiling point of not higher than 135 ℃ and is non-reactive with isocyanate; the polyisocyanates correspond to the general formula R (NCO)_nWherein R is one or more of the following: aliphatic hydrocarbons having 2 to 18 carbon atomsAn aromatic hydrocarbon group having 6 to 15 carbon atoms and an araliphatic hydrocarbon group having 8 to 15 carbon atoms, n being not less than 2; the polyisocyanate has an isocyanate group weight of 0.005 to 6 wt% based on the weight of the detergent. The invention also provides the adhesive product prepared by the method and the application of the adhesive product in the production of shoes.

The description of "first" and "second" of the first and second substrates of the present invention is merely for convenience of describing the two substrates, and is not intended to distinguish the order of the substrates.

The first substrate and the second substrate of the present invention may be the same or different.

The step a and the step b are not sequential, and can be performed simultaneously, or the step a can be performed first and then the step b can be performed, or the step b can be performed first and then the step a can be performed.

Cleaning agent

Preferably the polyisocyanate has an isocyanate group weight of from 0.007% to 5.6%, further preferably from 0.01% to 4.5%, still further preferably from 0.01% to 0.5%, yet further preferably from 0.02% to 0.2%, more preferably from 0.02% to 0.085%, most preferably from 0.04% to 0.085% by weight of the detergent.

The polar organic solvent of the present invention refers to a solvent in which the solvent molecules are polar molecules.

The boiling point of the polar organic solvent is preferably 35 to 135 ℃.

The polar organic solvent is preferably one or more of acetone, methyl ethyl ketone, ethyl acetate or butyl acetate, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of methyl ethyl ketone and propylene glycol diacetate, or a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate.

The polar solvent is further preferably a mixture of methyl ethyl ketone and ethyl acetate, a mixture of methyl ethyl ketone and butyl acetate, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of acetone and butyl acetate, a mixture of ethyl acetate and butyl acetate and methyl ethyl ketone, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate, methyl ethyl ketone or butyl acetate.

Most preferably, the polar solvent is methyl ethyl ketone.

Said general formula R (NCO)_nWherein n is preferably 2.5 to 5.5, most preferably 2.5 to 4.

The polyisocyanate is preferably one or more of the following: derivatives of aliphatic polyisocyanates having allophanate, biuret, uretdione, isocyanurate and/or iminooxadiazinedione groups, derivatives of aromatic polyisocyanates having allophanate, biuret, uretdione, isocyanurate and/or iminooxadiazinedione groups, and derivatives of cycloaliphatic polyisocyanates having allophanate, biuret, uretdione, isocyanurate and/or iminooxadiazinedione groups, further preferably one or more of the following: derivatives of aliphatic polyisocyanates having allophanate and/or isocyanurate groups, derivatives of cycloaliphatic polyisocyanates having allophanate and/or isocyanurate groups, and derivatives of aromatic polyisocyanates having allophanate and/or isocyanurate groups, with preference given to one or more of the following: toluene diisocyanate trimer, prepolymers of toluene diisocyanate and diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, prepolymers of diphenylmethane diisocyanate and tris (p-isocyanatophenyl) thiophosphate, most preferably one or more of the following: prepolymers of toluene diisocyanate and diphenylmethane diisocyanate, and trimers of toluene diisocyanate.

The solids content of the polyisocyanate is preferably from 25% by weight to 100% by weight, based on 100% by weight of the polyisocyanate.

The viscosity of the polyisocyanate is preferably from 3mPa.s to 5500mPa.s, most preferably from 3mPa.s to 2200mPa.s, according to DIN EN ISO 3219: 1994-10 at 23 deg.C, shear rate of 10s^-1The following measurements were made.

The NCO group content of the polyisocyanates is preferably from 4.5% to 24% by weight, most preferably from 4.5% to 14% by weight, in accordance with DIN-EN ISO 11909: 2007-05 was measured volumetrically and the measured data included free and potentially free NCO content.

The isocyanate functionality of the polyisocyanate is preferably 2 to 5.

The polyisocyanates preferably have a number-average molecular weight of 380g/mol to 1560g/mol, and are prepared by gel permeation chromatography in accordance with DIN 55672-1: 2016-03 was assayed at 23 ℃ against a polystyrene standard using tetrahydrofuran as the mobile phase.

The cleaning agent comprises a polar organic solvent and polyisocyanate, wherein the polar organic solvent is preferably a mixture of methyl ethyl ketone and ethyl acetate, a mixture of methyl ethyl ketone and butyl acetate, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of acetone and butyl acetate, a mixture of ethyl acetate and butyl acetate and methyl ethyl ketone, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate, methyl ethyl ketone or butyl acetate; the polyisocyanate is preferably one or more of the following: toluene diisocyanate trimer, prepolymers of toluene diisocyanate and diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, prepolymers of diphenylmethane diisocyanate and tris (p-isocyanatophenyl) thiophosphate; the polyisocyanate has an isocyanate group weight of 0.005 to 6 wt% based on the weight of the detergent.

Most preferably, the cleaner comprises methyl ethyl ketone and a polyisocyanate having an isocyanate functionality of from 2.5 to 4, the polyisocyanate being one or more of: a prepolymer of toluene diisocyanate and diphenylmethane diisocyanate, and a trimer of toluene diisocyanate, the isocyanate groups of the polyisocyanate being from 0.04% to 0.085% by weight of the detergent.

The cleaning agent does not contain a binder.

The polar solvent and the polyisocyanate of the present invention may be stored separately or may be mixed in advance and present in the form of a polyisocyanate solution.

First of allBase material

The first substrate is those commonly used in the art, in particular materials that can be used in midsoles, uppers and toes. The first substrate is preferably one or more of the following: polyurethane-based materials and polyvinyl chloride-based materials, most preferably polyurethane-based synthetic leather.

Adhesive agent

The adhesive may be a one-component adhesive, a two-component adhesive or a three-component adhesive commonly used in the art.

The binder is preferably one or more of the following: solvent-based polyurethane, solvent-based polychloroprene rubber, aqueous polyurethane dispersion, aqueous polychloroprene rubber and hot melt adhesive polyurethane, with aqueous polyurethane dispersion being more preferred, and two-component aqueous polyurethane dispersion being most preferred.

The two-component aqueous polyurethane dispersion preferably comprises an aqueous polyurethane dispersion and an isocyanate curing agent.

Second base material

The second substrate is those commonly used in the art, in particular materials that can be used in midsoles, uppers and toes. The second substrate is preferably one or more of the following: polyurethane-based materials and polyvinyl chloride-based materials, most preferably polyurethane-based synthetic leather.

Pretreatment of the second substrate

Preferably, the second substrate is pre-treated prior to application of the adhesive, comprising the steps of:

i. polishing or cleaning the second substrate; and

ii applying a primer to the second substrate treated in step i.

The polishing is used to increase the surface roughness of the substrate. The grinding may be mechanical grinding.

The cleaning is the removal of oil or dirt from the surface of the substrate using solvents, which are well known to those skilled in the art.

The primer may be a primer commonly used in the art, including but not limited to TCI coatings, UV coatings, solvent-borne polyurethane coatings, or aqueous polyurethane dispersion coatings.

Application of

The application may be to apply the cleaning agent or adhesive to the entire surface of the substrate or only to one or more portions of the surface of the substrate.

The application can be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transfer printing, preferably brushing, dipping or spraying.

Drying

The drying of the first substrate surface to which the cleaning agent is applied and the drying of the second substrate surface to which the adhesive is applied may refer to drying only the substrate surface, or may refer to drying a part of or the whole of the substrate including the substrate surface to which the cleaning agent or the adhesive is applied.

The drying may remove volatile components. The volatile component may be water.

The drying is preferably one or more of the following: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.

The higher the temperature of the drying, the better, but should not be above the temperature limit at which the substrate deforms in an uncontrolled manner or suffers other damage.

Contact with

Preferably, before the step c, the surface of the second substrate applied with the adhesive, which is treated by the step b, is thermally activated, and the thermal activation temperature is 45-75 ℃.

The thermal activation may be oven activation or infrared activation.

The contact is preferably performed before the temperature of the surface of the second substrate is lowered below the temperature at which the adhesive can adhere, and more preferably before the temperature of the surface of the second substrate is not lower than 60 ℃.

The first substrate is not treated with an adhesive prior to contacting the second substrate.

Adhesive article

The adhesive article is preferably footwear.