An RPVB glue, a composite carrier prepared by using the RPVB glue, and an application thereof

Abstract

This application relates to the technical field of the preparation of aqueous PVB adhesives, in particular to an RPVB glue, a composite carrier prepared by using the RPVB glue, and its application. An RPVB glue is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60 - 180 parts of aqueous polyurethane prepolymer, 1 - 5 parts of adhesion promoter, 0.5 - 2 parts of drier, 2 - 6 parts of aqueous crosslinking agent, and 1 - 5 parts of pH regulator; each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04 - 0.12 moL of -NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100 - 120 parts of deionized water, 5 - 20 parts of non-ionic emulsifier, 10 - 30 parts of cosolvent, and 1 - 3 parts of defoamer. This application not only has good environmental protection, but also has good mechanical properties, wear resistance, and hydrolysis resistance.

Description

Technical Field

[0001] This application relates to the technical field of the preparation of aqueous PVB adhesives, and in particular to an RPVB glue, a composite carrier prepared using the RPVB glue, and its applications. Background Art

[0002] Polyvinyl butyral PVB resin is prepared from polyvinyl alcohol PVA and butyraldehyde. It has excellent transparency, good solubility, and good light resistance, water resistance, heat resistance, cold resistance, and film-forming properties. The functional groups it contains can undergo various reactions such as saponification of acetyl groups, acetylation and sulfonation of hydroxyl groups, and have a high adhesion force to materials such as glass and metals (especially aluminum). Therefore, it has been widely used in the fields of manufacturing laminated safety glass, adhesives, ceramic transfer papers, aluminum foil papers, electrical materials, fiberglass products, fabric treatment agents, etc., and has become an indispensable synthetic resin material.

[0003] The related technical application No. 202210000272.6 discloses an aqueous PVB emulsion, which includes the following components by weight: 100 parts of PVA, 10 - 30 parts of water-soluble polyhydroxy compound, 30 - 50 parts of butyraldehyde, 5 - 20 parts of water-soluble aldehyde, 10 - 20 parts of hydrochloric acid, 10 - 20 parts of liquid caustic soda, 150 - 500 parts of deionized water, and 0.2 - 0.5 part of antioxidant. In the present invention, a hydrophilic compound that can participate in the reaction is directly added to the reaction of PVA solution and butyraldehyde. After the reaction, the residual aldehyde reactants are distilled out, and the aqueous RPVB emulsion is directly obtained.

[0004] Regarding the related technical aqueous PVB emulsion, the applicant found that the technical solution has the following defects: Although the aqueous PVB emulsion is prepared in a more environmentally friendly manner, when the prepared aqueous PVB emulsion is applied to fabric treatment, there are the following defects: The material properties and abrasion resistance of the film formed by the aqueous PVB emulsion are relatively poor compared to the film formed by solvent-based PVB, which limits its application in the field of fabric treatment. Summary of the Invention

[0005] In order to solve the above technical problems, this application provides an RPVB glue, a composite carrier prepared using the RPVB glue, and its applications.

[0006] In the first aspect, an RPVB glue provided by this application is achieved through the following technical solutions:

[0007] An RPVB glue is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60 - 180 parts of aqueous polyurethane prepolymer, 1 - 5 parts of adhesion promoter, 0.5 - 2 parts of dryer, 2 - 6 parts of aqueous crosslinking agent, and 1 - 5 parts of pH regulator; the solid content of the aqueous polyurethane prepolymer is 30 - 50%, and each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04 - 0.12 moL of -NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100 - 120 parts of deionized water, 5 - 20 parts of non-ionic emulsifier, 10 - 30 parts of cosolvent, and 1 - 3 parts of defoamer.

[0008] By adopting the above technical solution, the prepared RPVB glue not only has good environmental protection performance, but also has good mechanical properties, wear resistance and hydrolysis resistance.

[0009] Preferably, the non-ionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, and fatty amine polyoxyethylene ether; the fatty alcohol polyoxyethylene ether is at least one of AEO7, MOA-7, and AEO9; the fatty acid polyoxyethylene ester is at least one of A103, A105, and A110; the fatty amine polyoxyethylene ether is at least one of AC-1200 and AC-1800; the cosolvent is composed of acetone and plasticizer; the mass ratio of acetone to plasticizer is (6 - 8):(1 - 2); the plasticizer is di-n-hexyl adipate + triethylene glycol bis(2-ethylbutyrate); the defoamer is TEGO Degussa Foamex 825 defoamer emulsion or Foamex 1488 defoamer emulsion.

[0010] By adopting the above technical solution, the quality of the prepared RPVB glue can be guaranteed. In addition, while reducing the production and processing difficulty, the quality of the prepared RPVB glue can be guaranteed. Although a certain amount of acetone is used as the solvent for RPVB powder in this application, the final aqueous RPVB emulsion does not contain solvent acetone, and the environmental protection performance is relatively good.

[0011] Preferably, the preparation method of the RPVB powder includes the following steps:

[0012] Step 1: Recycle waste automotive windshield glass, cut off the black part beside the product, separate the black glass and the transparent glass. Only the transparent glass can be sold at a good price. The PVB part is also separated into black and white at the same time. The PVB product is crushed for the first time into a net shape to facilitate soaking and improve cleanliness.

[0013] Step 2: Immerse the products in the pool. They must be neatly arranged and stacked to facilitate subsequent operations. The immersion time is 15 - 18 days. The immersion area requires multi-channel immersion to enable cyclic operation;

[0014] Step 3: Second crushing: Crush the products to make the cleanliness of the products reach over 90%, then lay them flat and grind and brush the surface to increase the cleanliness of the products to over 95%;

[0015] Step 4: Cut the products obtained in Step 3 into strip-like noodles to further improve the cleanliness of the products. The cleanliness of the processed products is above 98%;

[0016] Step 5: Place the products into a cleaning machine to raise the cleanliness of the products to 100%;

[0017] Step 6: Granulate to remove moisture, with the moisture content below 0.01% to obtain RPVB powder.

[0018] By adopting the above technical solutions, the RPVB powder is recycled, with high resource utilization rate and good environmental protection performance. Moreover, the preparation method of the RPVB powder provided in this application is relatively simple and convenient for industrial production.

[0019] Preferably, the aqueous polyurethane prepolymer is prepared from the following raw materials: diisocyanate, polyol, chain extender, bismuth octoate, acetone, deionized water; the molar ratio of the polyol to the chain extender is 1:(2.6 - 3.2); the chain extender is 1,4-butanediamine, diethyltoluenediamine, 1,6-hexanediol; the polyol is a high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000 - 2000, a polycarbonate diol PCDL with a molecular weight of 2000 - 3000, and a modified PTMEG CPOL-MM-200 with a molecular weight of 1950 - 2050; the molar ratio of the high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000 - 2000, the polycarbonate diol PCDL with a molecular weight of 2000 - 3000, and the modified PTMEG CPOL-MM-200 with a molecular weight of 1950 - 2050 is (4 - 6):(3 - 4):(1 - 3); the molar amount of -NCO in the diisocyanate is 0.08 - 0.20 mol more than the total molar amount of active functional groups in the polyol and the chain extender.

[0020] By adopting the above technical solutions, the compound use of the aqueous polyurethane prepolymer and the aqueous RPVB emulsion can improve the overall physical properties, weather resistance, wear resistance, and environmental protection performance.

[0021] Preferably, the adhesion promoter is TEGO AddBond DS 1300 or TEGO AddBond 1270; the drying agent is Valirex Aqua Mix 353 or Valirex Aqua Mix 236; the aqueous crosslinking agent is Crosslinker CX-100 in combination with at least one of Desmodur XP-2802, Dispex Ultra FA-4416, and Dispex Ultra FA-4437; the pH regulator is one of VANTEX-T, Dow AMP-95, and Rhodoline AN-130.

[0022] By adopting the above technical solution, the combined use of the aqueous crosslinking agent and the adhesion promoter can ensure the bonding stability and mechanical properties between the present application and the composite substrate; the addition of the drying agent can accelerate the film-forming speed and improve the production efficiency of the composite carrier.

[0023] Preferably, the preparation method of the RPVB glue includes the following steps:

[0024] Step 1, preparation of the aqueous RPVB emulsion and the aqueous polyurethane prepolymer;

[0025] Step 2, after accurately measuring and mixing the aqueous RPVB emulsion and the aqueous polyurethane prepolymer in Step 1 evenly, sequentially add the accurately measured adhesion promoter, aqueous crosslinking agent, and drying agent, and mix evenly at 10-25°C and 0.02-0.08 MPa, then add the pH regulator to adjust the pH value of the system to 6.5-7.2 to obtain the finished RPVB glue.

[0026] The preparation method of the RPVB glue in the present application is relatively simple and convenient for realizing industrial mass production.

[0027] Preferably, the preparation method of the aqueous RPVB emulsion: dissolve the RPVB powder in the co-solvent, add deionized water, defoamer, and non-ionic emulsifier, emulsify and disperse at high speed, and remove the organic solvent by vacuum distillation to obtain the finished aqueous RPVB emulsion.

[0028] The preparation method of the aqueous RPVB emulsion in the present application is relatively simple and convenient for realizing industrial mass production.

[0029] Preferably, the preparation method of the aqueous polyurethane prepolymer is as follows: First, weigh polyol, diisocyanate, and bismuth octoate according to the formula, mix them evenly, then heat up to 85-90 °C and react for 2-3 h. Then add the chain extender and react at 70-80 °C for 1.5 h. Detect the content of NCO in the system, and detect the content of NCO in the system every 10 minutes. When the content of unreacted NCO in each mole of diisocyanate detected is 0.04-0.12 moL, add acetone to dilute the viscosity, and at the same time cool down to 40-45 °C, add triethanolamine for neutralization. Finally, add deionized water and disperse it evenly at high speed, distill off acetone, and dropwise add deionized water to adjust the solid content to 30-50%, to obtain the finished product.

[0030] The preparation method of the aqueous polyurethane prepolymer given in this application is relatively simple, the equipment used is relatively existing and conventional, the production cost is relatively low, and it is convenient to realize industrial mass production.

[0031] In the second aspect, a composite carrier prepared by using RPVB glue provided by this application is realized through the following technical solutions:

[0032] A composite carrier prepared by using RPVB glue includes a base material, and the RPVB glue is coated on the surface of the base material and cured to form an RPVB glue layer; the base material is one of release paper and plastic film.

[0033] By adopting the above technical solutions, it is beneficial to the production and processing of the composite carrier and convenient for the composite carrier to be applied to the fabric field. The composite fabric prepared by using the composite carrier in this application has good mechanical properties, wear resistance, and hydrolysis resistance.

[0034] In the third aspect, the application of a composite carrier prepared by using RPVB glue to fabric is to press the composite carrier on the surface layer of the fabric, uncover and remove the base material, and compound the RPVB glue layer on the surface layer of the fabric.

[0035] By adopting the above technical solutions, the composite fabric prepared by using the composite carrier in this application has good mechanical properties, wear resistance, and hydrolysis resistance, and effectively improves the mechanical properties and weather resistance of the base material.

[0036] In summary, this application has the following advantages:

[0037] 1. The RPVB glue prepared in this application not only has good environmental protection, but also has good mechanical properties, wear resistance, and hydrolysis resistance. Moreover, the composite fabric prepared by using this application has good mechanical properties, wear resistance, and hydrolysis resistance, and effectively improves the mechanical properties and weather resistance of the base fabric.

[0038] 2. The preparation method of this application is relatively simple and convenient to realize industrial mass production. Detailed implementation mode

[0039] The present application will be further described in detail below in conjunction with comparative examples and examples.

[0040] The preparation method of RPVB powder includes the following steps:

[0041] Step 1, recycle waste automobile windshield, cut off the black part beside the automobile windshield product, separate the black glass and the transparent glass. Only the transparent glass can be sold at a good price. In addition, the PVB part is also separated into black and white at the same time. The collected PVB product is subjected to the first crushing treatment and crushed into a net shape to facilitate soaking and improve cleanliness.

[0042] Step 2, immerse the product crushed into a net shape in Step 1 into a pool. It must be neatly arranged and stacked to facilitate subsequent operations. The soaking time is 15 days. The soaking solution is a 5 g / L aqueous solution of fatty acid polyoxyethylene ester non-ionic surfactant. The soaking area requires multi-channel soaking to achieve cyclic operation.

[0043] Step 3, second crushing: Crush the product obtained in Step 2 for the second time to make the product cleanliness reach more than 90%. Then lay it flat and grind and brush the impurities on the surface of the product to increase its cleanliness to more than 95%.

[0044] Step 4, cut the product obtained in Step 3 into strips like noodles to further improve the cleanliness of the product. The cleanliness of the processed product is above 98%.

[0045] Step 5, place the product into a cleaning machine to raise the product cleanliness to 100%.

[0046] Step 6, granulate to remove moisture. The moisture content is less than 0.01% to obtain the finished RPVB powder.

[0047] Preparation example

[0048] Preparation example 1

[0049] The aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 120 parts of deionized water, 12 parts of non-ionic emulsifier, 24 parts of co-solvent, and 1 part of defoamer. The particle size of the RPVB powder is controlled at 200 - 400 nm. The defoamer is Foamex 1488 defoamer emulsion. The non-ionic emulsifier is fatty alcohol polyoxyethylene ether AEO7. The co-solvent is 18 parts of acetone, 2 parts of di-n-hexyl adipate, and 4 parts of triethylene glycol-bis(2-ethyl)-butyrate.

[0050] The preparation method of the aqueous RPVB emulsion:

[0051] Step 1: Place accurately measured acetone, di-n-hexyl adipate, and triethylene glycol bis(2-ethylbutyrate) in a reaction kettle, stir at 240 rpm for 5 min, mix evenly to obtain a co-solvent, and set aside.

[0052] Step 2: Add RPVB powder to the reaction kettle, dissolve it in the co-solvent prepared in Step 1, add deionized water, Foamex 1488 antifoaming agent emulsion, and fatty alcohol polyoxyethylene ether AEO7, emulsify and disperse at high speed for 30 min, remove acetone by vacuum distillation, dropwise add deionized water, and emulsify and disperse at high speed to obtain a finished water-based RPVB emulsion with a solid content of 43.8%.

[0053] Preparation Example 2

[0054] The difference between Preparation Example 2 and Preparation Example 1 is that the particle size of RPVB powder is controlled within 400 - 800 nm.

[0055] Preparation Example 3

[0056] The difference between Preparation Example 3 and Preparation Example 1 is that the particle size of RPVB powder is controlled within 800 - 2000 nm.

[0057] Preparation Example 4

[0058] The difference between Preparation Example 4 and Preparation Example 1 is that the particle size of RPVB powder is controlled within 4 - 10 microns.

[0059] Preparation Example 5

[0060] The water-based polyurethane prepolymer is prepared from the following raw materials:

[0061] 234.24 g of diphenylmethane diisocyanate MDI,

[0062] 58.68 g of isophorone diisocyanate IPDI,

[0063] 166.67 g of high primary hydroxyl-modified polyether polyol P-1000 with a molecular weight of 1000,

[0064] 166.67 g of polycarbonate diol PCDL 1012 Polycarbonatediol with a molecular weight of 2000,

[0065] 55.56 g of BASF modified PTMEG CPOL-MM-200 with a molecular weight of 2000,

[0066] 25.47 g of 1,4-butanediamine,

[0067] 25.75 g of diethyl toluene diamine,

[0068] 34.14 g of 1,6-hexanediol,

[0069] 0.8 g of bismuth octanoate decanoate,

[0070] 360 g of acetone,

[0071] 3.8 g of triethanolamine,

[0072] 1800 g of deionized water.

[0073] The molar ratio of polyol to chain extender is 1:2.6.

[0074] The chain extender is 1,4-butanediamine, diethyltoluenediamine, 1,6-hexanediol.

[0075] The polyol is high primary hydroxyl group modified polyether polyol with a molecular weight of 1000, polycarbonate diol PCDL with a molecular weight of 2000, and modified PTMEG CPOL-MM-200 with a molecular weight of 2000, and the molar ratio is 6:3:1. The molar amount of -NCO in the diisocyanate is 0.08 - 0.20 mol more than the total molar amount of active functional groups in the polyol and chain extender.

[0076] Preparation method of aqueous polyurethane prepolymer:

[0077] Step 1: First, weigh 166.67 g of high primary hydroxyl group modified polyether polyol P-1000 with a molecular weight of 1000, 166.67 g of polycarbonate diol PCDL 1012Polycarbonatediol with a molecular weight of 2000, 55.56 g of BASF modified PTMEG CPOL-MM-200 with a molecular weight of 2000, 234.24 g of diphenylmethane diisocyanate MDI, 58.68 g of isophorone diisocyanate IPDI and 0.8 g of bismuth octanoate decanoate into the reaction kettle, and stir and mix at room temperature at 200 rpm for 10 min until evenly mixed;

[0078] Step 2: Heat up to 88.5 - 89.3 °C and react for 150 min, then add 25.47 g of 1,4-butanediamine, 25.75 g of diethyltoluenediamine, 34.14 g of 1,6-hexanediol, adjust the kettle temperature to 75.8 - 76.3 °C, after reacting for 90 min, detect the content of NCO in the system, detect the content of NCO in the system every 10 min. When the content of unreacted NCO in each mole of diisocyanate is within the range of 0.12 - 0.15 moL, add 360 g of acetone to dilute the viscosity, at the same time cool down to 40 °C, add 3.8 g of triethanolamine for neutralization, and finally add 1800 g of deionized water and disperse evenly at high speed,

[0079] Step 3: Distill off acetone, add deionized water dropwise, disperse evenly at high speed, and adjust the solid content to 42.0% to obtain the finished aqueous polyurethane prepolymer.

[0080] Preparation Example 6

[0081] The difference between Preparation Example 6 and Preparation Example 1 is that the polyols are high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000, polycarbonate diol PCDL with a molecular weight of 2000, and modified PTMEG CPOL-MM-200 with a molecular weight of 2000, and the molar ratio is 4:4:3.

[0082] Preparation Example 7

[0083] The difference between Preparation Example 7 and Preparation Example 1 is that the polyols are high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000, polycarbonate diol PCDL with a molecular weight of 2000, and modified PTMEG CPOL-MM-200 with a molecular weight of 2000, and the molar ratio is 45:40:15.

[0084] Preparation Example 8

[0085] The difference between Preparation Example 8 and Preparation Example 1 is that the polyols are high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000, polycarbonate diol PCDL with a molecular weight of 2000, and modified PTMEG CPOL-MM-200 with a molecular weight of 2000, and the molar ratio is 40:40:20.

[0086] Preparation Example 9

[0087] The difference between Preparation Example 9 and Preparation Example 8 is that the polyols are high primary hydroxyl group-modified polyether polyol with a molecular weight of 2000, polycarbonate diol PCDL with a molecular weight of 3000, and modified PTMEG CPOL-MM-200 with a molecular weight of 2000.

[0088] Preparation Example 10

[0089] The difference between Preparation Example 10 and Preparation Example 9 is that the chain extender is 1,4-butanediamine, perfluoro-2,5-dimethyl-3,6-dioxaoctanoic acid, 1,6-hexanediol. The molar ratio of 1,4-butanediamine, perfluoro-2,5-dimethyl-3,6-dioxaoctanoic acid (CAS NO.: 2479-74-5), and 1,6-hexanediol is 4:1:5.

[0090] The aqueous polyurethane prepolymer is prepared from the following raw materials:

[0091] 234.24 g of diphenylmethane diisocyanate MDI,

[0092] 58.68 g of isophorone diisocyanate IPDI,

[0093] 222.22 g of high primary hydroxyl modified polyether polyol P-2000 with a molecular weight of 2000,

[0094] 333.33 g of polycarbonate diol PCDL (UBE PH300) with a molecular weight of 3000,

[0095] 111.11 g of BASF modified PTMEG CPOL-MM-200 with a molecular weight of 2000,

[0096] 25.47 g of 1,4-butanediamine,

[0097] 32.22 g of perfluoro-2,5-dimethyl-3,6-dioxaoctanoic acid,

[0098] 42.67 g of 1,6-hexanediol,

[0099] 1.0 g of bismuth octanoate,

[0100] 480 g of acetone,

[0101] 3.8 g of triethanolamine,

[0102] 4.2 g of triethanolamine,

[0103] 2465 g of deionized water.

[0104] Preparation method of aqueous polyurethane prepolymer:

[0105] Step 1: First, weigh 222.22 g of high primary hydroxyl modified polyether polyol P-2000 with a molecular weight of 1000, 333.33 g of polycarbonate diol PCDL (UBE PH300) with a molecular weight of 3000, 111.11 g of BASF modified PTMEG CPOL-MM-200 with a molecular weight of 2000, 234.24 g of diphenylmethane diisocyanate MDI, 58.68 g of isophorone diisocyanate IPDI and 1 g of bismuth octanoate and place them in a reaction kettle. Stir and mix at room temperature at 240 rpm for 12 min until evenly mixed;

[0106] Step 2: Heat up to 88.7 - 89.5 °C and react for 150 min. Then add 25.47 g of 1,4 - butanediamine, 32.22 g of perfluoro - 2,5 - dimethyl - 3,6 - dioxaoctanoic acid, and 42.67 g of 1,6 - hexanediol. After adjusting the kettle temperature to 75.5 - 76.1 °C and reacting for 90 min, detect the content of NCO in the system. Detect the content of NCO in the system every 10 min. When the content of unreacted NCO in each mole of diisocyanate is within the range of 0.12 - 0.15 moL, add 480 g of acetone to dilute the viscosity, cool down to 40 °C at the same time, add 4.2 g of triethanolamine for neutralization, and finally add 2465 g of deionized water and disperse evenly at high speed.

[0107] Step 3: Distill off acetone, drop - wise add deionized water, disperse evenly at high speed, and adjust the solid content to 41.8% to obtain the finished aqueous polyurethane prepolymer.

[0108] Preparation Example 11

[0109] The difference between Preparation Example 11 and Preparation Example 1 is that the chain extender is 1,4 - butanediamine and 1,6 - hexanediol, and the molar ratio of 1,4 - butanediamine to 1,6 - hexanediol is 1:1.

[0110] Preparation Example 12

[0111] The difference between Preparation Example 12 and Preparation Example 1 is that the polyol is polycarbonate diol PCDL (UBE PH300).

[0112] Preparation Example 13

[0113] The difference between Preparation Example 13 and Preparation Example 1 is that the polyol is BASF modified PTMEG CPOL - MM - 200 with a molecular weight of 2000.

[0114] Preparation Example 14

[0115] The difference between Preparation Example 14 and Preparation Example 1 is that the polyol is highly primary - hydroxyl - modified polyether polyol P - 2000 with a molecular weight of 2000.

[0116] Examples

[0117] Example 1

[0118] An RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 60 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 part of the drying agent - Valirex Aqua Mix 353, 3 parts of Crosslinker CX - 100, 1.5 parts of Dispex UltraFA - 4416, and 2 parts of the pH regulator - VANTEX - T.

[0119] A method for preparing an RPVB glue includes the following steps:

[0120] Step 1, preparation of the aqueous RPVB emulsion and the aqueous polyurethane prepolymer;

[0121] For the preparation of the aqueous RPVB emulsion, refer to Preparation Example 1;

[0122] For the preparation of the aqueous polyurethane prepolymer, refer to Preparation Example 5;

[0123] Step 2, after accurately measuring and mixing the aqueous RPVB emulsion and the aqueous polyurethane prepolymer in Step 1 evenly, sequentially add the accurately measured adhesion promoter, aqueous crosslinker, and drying agent, and mix evenly at 10 - 15°C and 0.02 MPa. Then add the pH regulator to adjust the pH value of the system to be between 6.8 and 7.2 to obtain the finished RPVB glue.

[0124] A composite carrier prepared using the RPVB glue includes a base material and an RPVB glue layer compounded on the base material. Among them, the formation method of the RPVB glue layer: The above - prepared RPVB glue is coated on the surface of the base material and cured to form the RPVB glue. The base material can be selected from one of release paper and plastic film. In this embodiment, release paper is preferably selected.

[0125] The composite carrier prepared using the RPVB glue is applied to the fabric. The composite carrier is pressed onto the surface layer of the fabric, the base material is peeled off and removed, and the RPVB glue layer is compounded on the surface layer of the fabric. The composite fabric prepared using the composite carrier has good mechanical properties, wear resistance, and hydrolysis resistance.

[0126] Example 2

[0127] Example 2 is different from Example 1 in that: An RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 100 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 part of the drying agent - Valirex Aqua Mix 353, 3 parts of Crosslinker CX-100, 1.5 parts of Dispex Ultra FA-4416, and 2 parts of the pH regulator - VANTEX-T.

[0128] Example 3

[0129] Example 3 is different from Example 1 in that: An RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 150 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 part of the drying agent - Valirex Aqua Mix 353, 3 parts of Crosslinker CX-100, 1.5 parts of Dispex Ultra FA-4416, and 2 parts of the pH regulator - VANTEX-T.

[0130] Example 4

[0131] Example 4 is different from Example 1 in that: An RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 180 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 part of the drying agent - Valirex Aqua Mix 353, 3 parts of Crosslinker CX-100, 1.5 parts of Dispex Ultra FA-4416, and 2 parts of the pH regulator - VANTEX-T.

[0132] Example 5

[0133] Example 5 is different from Example 1 in that: The aqueous RPVB emulsion in Preparation Example 1 is replaced by the aqueous RPVB emulsion in Preparation Example 2.

[0134] Example 6

[0135] Example 6 is different from Example 1 in that: The aqueous RPVB emulsion in Preparation Example 1 is replaced by the aqueous RPVB emulsion in Preparation Example 3.

[0136] Example 7

[0137] Example 7 is different from Example 1 in that the aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 6.

[0138] Example 8

[0139] Example 8 is different from Example 1 in that the aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 7

[0140] Example 9

[0141] Example 9 is different from Example 1 in that the aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 8

[0142] Example 10

[0143] Example 10 is different from Example 1 in that the aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 9.

[0144] Example 11

[0145] Example 11 is different from Example 1 in that the aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 10.

[0146] Example 12

[0147] Example 12 is different from Example 1 in that an RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 2, 120 parts of the aqueous polyurethane prepolymer in Preparation Example 10, 2.4 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.8 part of the drying agent - Valirex Aqua Mix 353, 3.6 parts of Crosslinker CX - 100, 1.2 parts of Dispex Ultra FA - 4416, and 1.8 parts of the pH regulator - VANTEX - T.

[0148] Comparative Example

[0149] Comparative Example 1

[0150] The difference between Comparative Example 1 and Example 1 lies in: An RPVB glue is prepared from the following raw materials by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 30 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 parts of the dryer - Valirex Aqua Mix 353, 3 parts of Crosslinker CX - 100, 1.5 parts of Dispex Ultra FA - 4416, and 2 parts of the pH regulator - VANTEX - T.

[0151] Comparative Example 2

[0152] The difference between Comparative Example 2 and Example 1 lies in: An RPVB glue is prepared from the following raw materials by weight: 100 parts of the aqueous RPVB emulsion in Preparation Example 1, 200 parts of the aqueous polyurethane prepolymer in Preparation Example 5, 2 parts of the adhesion promoter - TEGO AddBond DS 1300, 0.6 parts of the dryer - Valirex Aqua Mix 353, 3 parts of Crosslinker CX - 100, 1.5 parts of Dispex Ultra FA - 4416, and 2 parts of the pH regulator - VANTEX - T.

[0153] Comparative Example 3

[0154] The difference between Comparative Example 3 and Example 1 lies in: The aqueous RPVB emulsion in Preparation Example 1 is replaced with the aqueous RPVB emulsion in Preparation Example 4.

[0155] Comparative Example 4

[0156] The difference between Comparative Example 4 and Example 1 lies in: The aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 11.

[0157] Comparative Example 5

[0158] The difference between Comparative Example 5 and Example 1 lies in: The aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 12.

[0159] Comparative Example 6

[0160] The difference between Comparative Example 6 and Example 1 lies in: The aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 13.

[0161] Comparative Example 7

[0162] The difference between Comparative Example 7 and Example 1 lies in: The aqueous polyurethane prepolymer in Preparation Example 5 is replaced with the aqueous polyurethane prepolymer in Preparation Example 14.

[0163] Performance Detection Test

[0164] Detection Method / Test Method

[0165] 1. Mechanical Strength Test of Resin Film: Cure at 130°C to obtain the film to be tested. Conduct the test according to the test method of tensile strength and elongation at break of adhesive tape in GB / T 30776-2014. The testing equipment is Shimadzu universal testing machine AGS-X type. The test conditions are: temperature (23 + 2)°C, relative humidity (50 + 5)%.

[0166] 2. Weather Resistance Test: Conduct the test by the constant temperature and humidity hydrolysis resistance method according to the requirements of QB / T 4671-2014 "Test Methods for Artificial Leather and Synthetic Leather - Determination of Hydrolysis Resistance".

[0167] 3. Peel Strength Test: The base fabric is ultra-fine fiber paper, and the surface layer formed by the RPVB glue prepared in Examples 1-12 and Comparative Examples 1-7. Adopt the method of GB / T 2791-1995 "Adhesives - T Peel Strength Test Method - Flexible Material to Flexible Material" to test the peel strength of the surface layer formed by ultra-fine fiber paper and RPVB glue.

[0168] 4. Abrasion Resistance Test: Conduct the abrasion resistance test of the surface layer formed by the RPVB glue prepared in Examples 1-12 and Comparative Examples 1-7 according to the GMW 3208 - 2012 rotational wear test. Observe whether there is damage after 500 times of CS-10 1KG. If there is no damage after 500 times of CS-10 1KG, then conduct 800 times of CS-10 1KG and observe whether there is damage.

[0169] Data Analysis

[0170] Table 1 is the detection parameter table of Examples 1-12 and Comparative Examples 1-7

[0171]

[0172] Combined with Examples 1-12 and Comparative Examples 1-7 and Table 1, it can be seen that by comparing Examples 1-4 with Comparative Examples 1-2, the mechanical properties and peel strength of Examples 1-4 are better than those of Comparative Example 1, and the mechanical properties and peel strength of Examples 1-4 are relatively smaller than those of Comparative Example 2; the weather resistance of Examples 1-4 is better than that of Comparative Example 1 and relatively smaller than that of Comparative Example 2. Therefore, the RPVB glue prepared by using 100 parts of aqueous RPVB emulsion and 60-180 parts of aqueous polyurethane prepolymer has good environmental protection performance, and has good mechanical properties, wear resistance and hydrolysis resistance.

[0173] It can be seen from combining Examples 1-12 and Comparative Examples 1-7 and in conjunction with Table 1 that when comparing Examples 1, 5-6 with Comparative Example 3, it can be known that when the particle size of RPVB powder is controlled within 200-2000 nm, the RPVB glue prepared has good environmental protection performance, and has good mechanical properties, wear resistance, and hydrolysis resistance. The preferred solution for mechanical properties is that the particle size of RPVB powder is controlled within 200-400 nm. The preferred solution for economy is that the particle size of RPVB powder is controlled within 400-800 nm.

[0174] It can be seen from combining Examples 1-12 and Comparative Examples 1-7 and in conjunction with Table 1 that when comparing Examples 1, 7-11 with Comparative Examples 4-7, it can be known that an increase in the dosage of polycarbonate diol PCDL can improve the overall tensile strength, but has a negative impact on the tensile fracture rate. When used in combination with modified PTMEG CPOL-MM-200, it can reduce the impact of the decrease in the tensile fracture rate caused by the use of polycarbonate diol PCDL. Using high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000-2000, polycarbonate diol PCDL with a molecular weight of 2000-3000, and modified PTMEG CPOL-MM-200 with a molecular weight of 1950-2050 as polyols can ensure that the present application has good flexibility, tensile strength, and tensile fracture rate. The RPVB glue prepared with a molar ratio of (4-6):(3-4):(1-3) of high primary hydroxyl group-modified polyether polyol with a molecular weight of 1000-2000, polycarbonate diol PCDL with a molecular weight of 2000-3000, and modified PTMEG CPOL-MM-200 with a molecular weight of 1950-2050 has relatively better comprehensive performance.

[0175] It can be seen from combining Examples 1-12 and Comparative Examples 1-7 and in conjunction with Table 1 that when comparing Examples 1, 7-11 with Comparative Examples 4-7, it can be known that the mechanical properties of Example 11 are better than those of Example 10, but the peel strength of Example 11 has decreased. The peel strength of Example 11 is still greater than 30 N / 3 cm, and it can improve the overall anti-fouling performance and wear resistance, and is suitable as a surface layer material with anti-fouling and easy-cleaning requirements.

[0176] It can be seen from combining Examples 1-12 and Comparative Examples 1-7 and in conjunction with Table 1 that when comparing Example 1, Example 10 with Example 12, it can be known that the comprehensive performance of Example 10 is the best, and the performance of Example 12 is similar to that of Example 10, but its production cost is relatively lower. Considering the comprehensive cost and performance, Example 12 is the preferred solution of the present application.

[0177] This specific embodiment is only an explanation of the present application, and it is not a limitation to the present application. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this embodiment as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. An RPVB glue, characterized in that: It is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60 - 180 parts of aqueous polyurethane prepolymer, 1 - 5 parts of adhesion promoter, 0.5 - 2 parts of dryer, 2 - 6 parts of aqueous crosslinking agent, 1 - 5 parts of pH regulator; the solid content of the aqueous polyurethane prepolymer is 30 - 50%, and each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04 - 0.12 moL of -NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100 - 120 parts of deionized water, 5 - 20 parts of nonionic emulsifier, 10 - 30 parts of cosolvent, 1 - 3 parts of defoamer; the aqueous polyurethane prepolymer is prepared from the following raw materials: diisocyanate, polyol, chain extender, bismuth octoate, acetone, deionized water; the molar ratio of polyol to chain extender is 1:(2.6 - 3.2); the chain extender is 1,4 - butanediamine, diethyltoluenediamine, 1,6 - hexanediol; the polyol is a high - hydroxyl - modified polyether polyol with a molecular weight of 1000 - 2000, a polycarbonate diol PCDL with a molecular weight of 2000 - 3000, and a modified PTMEG CPOL - MM - 200 with a molecular weight of 1950 - 2050.

2. The RPVB glue according to claim 1, wherein: The nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, and fatty amine polyoxyethylene ether; the fatty alcohol polyoxyethylene ether is at least one of AEO7, MOA - 7, and AEO9; the fatty acid polyoxyethylene ester is at least one of A103, A105, and A110; the fatty amine polyoxyethylene ether is at least one of AC - 1200 and AC - 1800; the cosolvent is composed of acetone and a plasticizer; the mass ratio of acetone to plasticizer is (6 - 8):(1 - 2); the plasticizer is at least one of di - n - hexyl adipate and triethylene glycol bis(2 - ethyl)butyrate; the defoamer is TEGO Degussa Foamex 825 defoamer emulsion or Foamex1488 defoamer emulsion.

3. The RPVB glue according to claim 1 or 2, characterized in that: The preparation method of the RPVB powder includes the following steps: Step 1, Recycle waste automotive windshield glass, cut off the black part beside the product, separate the black glass and the transparent glass, and also separate the black and white parts of the PVB part. Conduct the first crushing of the PVB product into a net shape to facilitate soaking and improve cleanliness. Step 2, Immerse the product in a pool, arrange and stack it neatly to facilitate subsequent operations. The soaking time is 15 - 18 days, and multi - channel soaking and circulation operations are carried out in the soaking area. Step 3, Second crushing: Crush the product to make the cleanliness of the product reach more than 90%, then flatten it and grind and brush the surface to raise the cleanliness of the product to more than 95%. Step 4, Cut the product obtained in Step 3 into strip - like noodles to further improve the cleanliness of the product, and the cleanliness of the processed product is above 98%. Step 5, Place the product in a cleaning machine to raise the cleanliness of the product to 100%. Step 6: Granulation, removing moisture until the moisture content is lower than 0.01% to obtain RPVB powder.

4. An RPVB glue according to claim 1, characterized in that: The molar ratio of the highly primary hydroxyl group-modified polyether polyol with a molecular weight of 1000 - 2000, the polycarbonate diol PCDL with a molecular weight of 2000 - 3000, and the modified PTMEG CPOL-MM-200 with a molecular weight of 1950 - 2050 is (4 - 6):(3 - 4):(1 - 3); the molar amount of -NCO in the diisocyanate is 0.08 - 0.20 mol more than the total molar amount of the active functional groups in the polyol and the chain extender.

5. A RPVB glue according to claim 1, characterized in that: The adhesion promoter is TEGO AddBond DS 1300 or TEGO AddBond 1270; the drying agent is Valirex Aqua Mix 353 or Valirex Aqua Mix 236; the aqueous crosslinker consists of Crosslinker CX-100 and at least one selected from Desmodur XP-2802, Dispex Ultra FA-4416, and Dispex Ultra FA-4437; the pH regulator is one of VANTEX-T, Dow AMP-95, and Rhodoline AN-130.

6. The RPVB glue according to claim 1, characterized in that: The preparation method of the RPVB glue includes the following steps: Step 1: Preparation of the aqueous RPVB emulsion and the aqueous polyurethane prepolymer. Step 2: After accurately measuring and mixing the aqueous RPVB emulsion and the aqueous polyurethane prepolymer in Step 1 evenly, successively add the accurately measured adhesion promoter, aqueous crosslinker, and drying agent, and mix evenly at 10 - 25°C and 0.02 - 0.08 MPa, then add the pH regulator to adjust the pH value of the system to 6.5 - 7.2 to obtain the finished RPVB glue.

7. The RPVB glue according to claim 6, characterized in that: The preparation method of the aqueous RPVB emulsion: Dissolve the RPVB powder in the cosolvent, add deionized water, defoamer, and non-ionic emulsifier, emulsify and disperse at high speed, and remove the organic solvent by vacuum distillation to obtain the finished aqueous RPVB emulsion.

8. The RPVB glue according to claim 6, characterized in that: The preparation method of the aqueous polyurethane prepolymer: First weigh the polyol, diisocyanate, and bismuth octoate according to the formula, mix evenly, then heat up to 85 - 90°C and react for 2 - 3 h, then add the chain extender and react at 70 - 80°C for 1.5 h. Detect the content of NCO in the system, detect the content of NCO in the system every 10 min. When the content of unreacted NCO in each mole of diisocyanate detected is 0.04 - 0.12 moL, add acetone to dilute the viscosity, and at the same time cool down to 40 - 45°C, add triethanolamine for neutralization, finally add deionized water and disperse evenly at high speed, distill off acetone, and dropwise add deionized water to adjust the solid content to 30 - 50% to obtain the finished product.

9. A composite carrier prepared using the RPVB glue according to any one of claims 1-8, characterized in that: It includes a substrate, and the RPVB glue is coated on the surface of the substrate and cured to form an RPVB glue layer; the substrate is one of release paper and plastic film.

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