CN103805122A - Waterborne polyurethane patch adhesive and preparation method thereof - Google Patents
Waterborne polyurethane patch adhesive and preparation method thereof Download PDFInfo
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- CN103805122A CN103805122A CN201410053006.5A CN201410053006A CN103805122A CN 103805122 A CN103805122 A CN 103805122A CN 201410053006 A CN201410053006 A CN 201410053006A CN 103805122 A CN103805122 A CN 103805122A
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Abstract
The invention discloses a waterborne polyurethane patch adhesive, which adopts a technical formula comprising the following components in parts by weight: 100 parts of macro-molecular glycol, 1-3 parts of micro-molecular chain extender, 1-3 parts of micro-molecular cross linking agent, 30-80 parts of waterborne curing agent, 0.1-0.2 part of organic bismuth catalyst, 3-8 parts of 2,2-dimethylolpropionic acid (DMPA), 50-100 parts of AC (acetone), 2-6 parts of triethylamine, 30-40 parts of de-ionized water and 0.5-1.5 parts of polyamine. The patch adhesive disclosed by the invention has the advantages of being non-toxic, light in smell, free from combustion and explosion, low or free from volatile organic compound (VOC), strong in binding power, low in energy consumption, excellent in performance of coated product, environment-friendly and the like; the patch adhesive is consistent with current requirements on energy conservation and emission reduction, low-carbon lifestyle and novel environmental protection, and can completely replace the current solvent-type adhesive.
Description
Technical field
The present invention relates to synthetic leather material technology field, particularly a kind of PVC DB-921 aqueous polyurethane used for artificial leather patch glue and preparation method thereof.
Background technology
At present, in separate-type paper method PVC leatheroid production process, after PVC slurry film forming and the laminating of base cloth adopts solvent borne polyurethane tackiness agent substantially and from PVC slurry.Such PU resin all makes with solvent polymerization method as primary solvent by toluene, dimethylbenzene, acetone, butanone (MEK), ethyl acetate and dimethyl formamide (DMF) etc.These account for more than 60% organic solvent of whole resinous principle is all objectionable impurities, and the harm that human body is caused is many-sided.80% solvent cannot reclaim, and will be discharged into the river of periphery and day aerial by water and air, will certainly severe contamination local environment, and production, the life of giving people, the public's life and health forms significant threat.And its finished product has larger irritating smell.Stop from source to pollute, extremely urgent for leatheroid industry.Aqueous polyurethane is take water as medium, have nontoxic, smell is little, it is not quick-fried, low not fire or zero VOC, cohesive force is strong, low consumption and coated article excellent performance, the advantage such as environmentally friendly, meet current energy-saving and emission-reduction, low-carbon (LC) life, novel environment friendly requirement, will finally replace existing solvent-based adhesive.
Summary of the invention
The object of the present invention is to provide a kind of PVC aqueous polyurethane patch used for artificial leather glue and preparation method thereof, that the patch glue obtaining has is nontoxic, smell is little, it is not quick-fried, low not fire or zero VOC, cohesive force is strong, low consumption and coated article excellent performance, the advantage such as environmentally friendly, meet current energy-saving and emission-reduction, low-carbon (LC) life, novel environment friendly requirement, can replace existing solvent-based adhesive completely.
For reaching above object, the technical scheme that the present invention takes is: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 1～3 part of small molecule chain extender, 1～3 part of small molecules linking agent, waterborne curing agent 30-80 part, 0.1～0.2 part of organic bismuth catalyst, 3～8 parts of 2,2-dimethylol propionic acids (DMPA), 50～100 parts of AC (acetone), 2～6 parts of triethylamines, 30～40 parts of deionized waters, 0.5～1.5 part of polyamine.
Described macromolecular polyol is polyester, polyethers, or their mixture.
Described polyester is polyethylene glycol adipate, poly-diethylene glycol adipate, poly adipate succinic acid ester, or poly-hexanodioic acid hexylene glycol ester; Described polyethers is polypropylene glycol.
Described small molecule chain extender is ethylene glycol, glycol ether, or Isosorbide-5-Nitrae butyleneglycol.
Described small molecules linking agent is TriMethylolPropane(TMP).
Described waterborne curing agent is polyisocyanates, many aziridine, or aminoresin.
The preferred tolylene diisocyanate of described polyisocyanates (TDI), isophorone diisocyanate (IPDI); 20～50 parts of tolylene diisocyanates (TDI), 10～30 parts of isophorone diisocyanates (IPDI).
Described polyamine is quadrol, or diethylenetriamine.
For reaching above object, the technical scheme that the present invention takes is: a kind of PVC aqueous polyurethane patch used for artificial leather glue preparation method, being equipped with in the reactor of mechanical stirrer, thermometer, reflux exchanger, add macromolecular polyol, and at 100 ℃-120 ℃, 1hr dewaters under the condition of vacuum≤-0.8MPa, under 80 ℃ of conditions, add small molecule chain extender and the small molecules linking agent of metering, waterborne curing agent, organic bismuth catalyst is appropriate, reaction 3hr, NCO content in detection system, in the time that NCO content reaches theoretical value, be cooled to 60 ℃, add with 2 of N-Methyl pyrrolidone (NMP) dissolving, 2-dimethylol propionic acid (DMPA), and react 4-5hr at this temperature, survey NCO content adds AC (acetone) viscosity reduction while reaching theoretical value, obtain the performed polymer of NCO end-blocking, be cooled to≤add triethylamine after 50 ℃, after neutralization reaction number minute, under stirring, high speed dispersion adds the deionized water emulsification measuring, after add polyamine chain extension, vacuum decompression is sloughed acetone, make solid content and be 35% blue light emulsion aqueous polyurethane patch glue.
The patch glue that the present invention obtains adds the auxiliary agent such as defoamer and thickening material, adjusts the rubber cement of the required viscosity of realistic production.
That this kind of patch glue has is nontoxic, smell is little, it is not quick-fried, low not fire or zero VOC, cohesive force is strong, low consumption and coated article excellent performance, the advantage such as environmentally friendly, meet current energy-saving and emission-reduction, low-carbon (LC) life, novel environment friendly requirement, can replace existing solvent-based adhesive completely.
The application art of this kind of patch glue is as follows: separate-type paper → coating surface layer → oven dry → coating PVC foaming layer → oven dry → coating tack coat → wet combining base cloth → oven dry → cooling → peel off → bundling aftertreatment.
Embodiment
Embodiment mono-: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 1～3 part of small molecule chain extender, 1～3 part of small molecules linking agent, waterborne curing agent 30-80 part, 0.1～0.2 part of organic bismuth catalyst, 2,3～8 parts of 2-dimethylol propionic acids (DMPA), 50～100 parts of AC (acetone), 2～6 parts of triethylamines, 30～40 parts of deionized waters, 0.5～1.5 part of polyamine.
Embodiment bis-: a kind of PVC aqueous polyurethane patch used for artificial leather glue preparation method, being equipped with in the reactor of mechanical stirrer, thermometer, reflux exchanger, add macromolecular polyol, and at 100 ℃-120 ℃, 1hr dewaters under the condition of vacuum≤-0.8MPa, under 80 ℃ of conditions, add small molecule chain extender and the small molecules linking agent of metering, waterborne curing agent, organic bismuth catalyst is appropriate, reaction 3hr, NCO content in detection system, in the time that NCO content reaches theoretical value, be cooled to 60 ℃, add with 2 of N-Methyl pyrrolidone (NMP) dissolving, 2-dimethylol propionic acid (DMPA), and react 4-5hr at this temperature, survey NCO content adds AC (acetone) viscosity reduction while reaching theoretical value, obtain the performed polymer of NCO end-blocking, be cooled to≤add triethylamine after 50 ℃, after neutralization reaction number minute, under stirring, high speed dispersion adds the deionized water emulsification measuring, after add polyamine chain extension, vacuum decompression is sloughed acetone, make solid content and be 35% blue light emulsion aqueous polyurethane patch glue.
Viscosimetric analysis: with NDJ-4 type rotational viscosimeter, by GB2794-1995, wherein bath temperature is 25 ± 1 ℃.Water tolerance is measured: take a certain amount of glued membrane (W1) and be immersed in 20 ℃ of distilled water, take out at interval of for some time, dry surface-moisture with filter paper, the quality that weigh immediately (W2) absorbs moisture by the glued membrane of unit mass is that water-intake rate P (%) represents: P (%)=[(W2-E1)/W1] × 100%.
T-shaped stripping strength is measured: with T stripping means, bond samples is implemented to pulling force, the required merit of unit width while making bond samples produce bond damage.Generally, with N/cm, N/m or KN/m are unit.According to GB2791-1995, the sample of test PVC leatheroid is long is 150mm, and wide is 30 ± 0.2mm.Draw speed is 100mm/min.
Resistance to toluene test: toluene is coated in to the cloth basal plane of PVC sample, then carries out T-shaped stripping strength mensuration with electronic tensile machine.
Solid content test: about 2g emulsion sample is put into the flat glass dish that diameter is 4cm, close the lid, weigh, then base is placed in to stink cupboard, after most of moisture volatilization, moves into and establish in ventilate baking oven, at 115 ℃, be dried to constant weight, can calculate solid content.Solid content=(M1-M)/M0 × 100%.
Tensile strength and test of elongation rate: glued membrane is made to the dumbbell shaped of 40mm × 3mm, tested its tensile strength and elongation with smart electronics puller system, draw speed is 200mm/min.
Aqueous polyurethane is by soft section and the hard section of macromolecular compound forming, and soft section is made up of macromolecular polyol, and hard section is made up of carbamate and polar link.In experiment, different types of macromolecular polyol, small molecule chain extender and linking agent have a great impact emulsion and glue film performance.
Macromolecular polyol.Other conditions are constant, only change soft section of kind.Macromolecular polyol divides: polyester (polyethylene glycol adipate, poly-diethylene glycol adipate, poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester; Polyethers (polypropylene glycol), ester ether mix.
Table 1 macromolecular polyol affects emulsion and glue film performance:
As can be seen from Table 1, polyvalent alcohol is little to the appearance effects of emulsion.The synthetic glued membrane of polyester PL2000 shows comparatively outstanding aspect stripping strength, solid content and water-intake rate, is mainly that the molecular force between soft chain segment is large because macromolecular structure is regular, and crystallinity is strong, and cohesive force is high; And crystallinity is conducive to the formation of interspaces, the infiltration of prevention water molecules, swelling; Its water-intake rate is better than polyether-type, but ester bond polarity is larger, and intermolecular reactive force is greater than the reactive force between pfpe molecule, and snappiness is poor, inadaptable be used in snappiness and require in high product.Polyether 220 N, because containing ehter bond, more easily rotates, and snappiness is good, and elongation is high; But internal cohesive energy is less than the internal cohesive energy of polyester, and stripping strength is low, and water-intake rate is large, rub the product of clothing leather aspect so also should not be used in water.Its good hydrophilic property of polyester type, polyether-type wetting ability is poor, so the synthetic solid content of PL2000 is higher than Polyether 220 N.And ester ether mixes between between the two, over-all properties is better, can be common for products such as clothing leather, sofa artificial leather and luggage leathers.In actual production, according to the performance of variant production and requirement, select suitable macromolecular polyol.
Small molecule chain extender and linking agent.In aqueous polyurethane building-up process, can introduce small molecule chain extender and linking agent, object is to improve glue film performance.
Table 2 small molecule chain extender and linking agent affect emulsion and glue film performance:
As can be seen from Table 2,, containing the emulsion of chainextender and linking agent, properties is all not poor through people's will; The aqueous polyurethane that only adds chainextender is linear structure, thermoplasticity is large, generate urethano and urea groups, finished product has higher stripping strength, hardness, elongation at break and cohesive strength, aspect stripping strength and rate elongation, be better than single WPU containing linking agent, especially in cohesive force, performance is comparatively outstanding, but has the shortcomings such as poor water resistance, solvent resistance be bad.Only, containing the introducing because of linking agent in the WPU of linking agent, make polyurethane molecular produce branch point, form reticulated structure, improved water-fast, solvent resistance, therefore, aspect tensile strength and water-intake rate, be better than the WPU containing chainextender.But due to crosslinked action, force of cohesion is excessive, and molecular motion is fettered, in the time being subject to heating, intermolecular can not rearranging, can not form reactive force with adherend surface, so be not so good as the WPU containing chainextender in cohesive force.Add the chainextender of suitable proportion and the WPU of linking agent simultaneously, on properties, all show comparatively balanced.
The ratio of n (Nco)/n (OH) is on emulsion and glue film performance impact.In prepolymer reaction, fix other reaction conditionss constant, only change the ratio of n (Nco)/n (OH), thereby draw the result of different performance.
The ratio of table 3n (Nco)/n (OH) affects emulsion and glue film performance:
| R value | Emulsion appearance | Elongation/% | Water-intake rate/% | Tensile strength/MPa |
| 2.0 | Blue transparent | 586.35 | 18.53 | 3.5762 |
| 3.0 | Translucent | 502.72 | 12.17 | 4.5613 |
| 4.0 | Semi-transparent blue phase | 430.31 | 9.3 | 5.3417 |
| 5.0 | Opal blue phase | 320.51 | 10.8 | 5.8961 |
| 6.0 | Milky white | 280.62 | 13.26 | 6.8762 |
As can be seen from Table 3, along with the increase of the ratio of n (Nco)/n (OH), emulsion appearance is by the transparent oyster white that gradually becomes, and the tensile strength of glued membrane increases, and it is large that hardness becomes, and elongation at break reduces along with the increase of ratio; Illustrate that in molecular chain, rigid radical increases, soft segment reduces, and intermolecular and intramolecular hydrogen bond density increases.Increasing of urea key increases hard section in cross-linking density and macromolecular structure, and water resistance improves.By the variation of soft, hard section ratio, glued membrane can be from soft to firmly regulating, to adapt to the requirement of variant production to feel.
Waterborne curing agent is introduced.Requiring (as water is rubbed clothing leather, footwear leather) in heat-resisting water, the more better products of resistance to strong solvent, can add waterborne curing agent further to promote its glue film performance.
Table 4 waterborne curing agent affects glue film performance:
| Waterborne curing agent | T stripping strength/N/cm | Tensile strength/MPa | Elongation/% | Water-intake rate/% |
| Blank | 4.38 | 8.32 | 468.25 | 8.67 |
| 2％ | 5.87 | 10.22 | 413.05 | 5.63 |
| 4％ | 8.16 | 12.46 | 328.19 | 3.28 |
| 6％ | 10.64 | 15.13 | 267.35 | 2.65 |
| 8％ | 11.75 | 17.86 | 230.57 | 3.52 |
As can be seen from Table 4, along with the increase of waterborne curing agent consumption, glued membrane has stripping strength, tensile strength to improve constantly, and water-intake rate and elongation constantly reduce.This is because the functional group of waterborne curing agent reacts with hydroxyl, carboxyl, amido and urea groups in urethane, produces three-dimensional cross-linked reticulated structure, and it is large that force of cohesion and cross-linking density become, and the performance of glued membrane is strengthened.Waterborne curing agent is that water dispersibles polyisocyanates, many aziridine, aminoresin.
Embodiment tri-: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 1 part of small molecule chain extender, 1 part of small molecules linking agent, 30 parts of waterborne curing agents, 0.1 part of organic bismuth catalyst, 2,3 parts of 2-dimethylol propionic acids (DMPA), 50 parts of AC (acetone), 2 parts of triethylamines, 30 parts of deionized waters, 0.5 part of polyamine.
Embodiment tetra-: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 3 parts of small molecule chain extenders, 3 parts of small molecules linking agents, 80 parts of waterborne curing agents, 0.2 part of organic bismuth catalyst, 2,8 parts of 2-dimethylol propionic acids (DMPA), 100 parts of AC (acetone), 6 parts of triethylamines, 40 parts of deionized waters, 1.5 parts of polyamines.
Embodiment five: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 2 parts of small molecule chain extenders, 2 parts of small molecules linking agents, 55 parts of waterborne curing agents, 0.15 part of organic bismuth catalyst, 2,5.5 parts of 2-dimethylol propionic acids (DMPA), 75 parts of AC (acetone), 4 parts of triethylamines, 35 parts of deionized waters, 1 part of polyamine.
Embodiment six: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of polyethylene glycol adipates, 2 parts of ethylene glycol, 1 part of TriMethylolPropane(TMP), 20 parts of tolylene diisocyanates (TDI), 10 parts of isophorone diisocyanates (IPDI), 0.1 part of organic bismuth catalyst, 5 parts of 2,2-dimethylol propionic acids (DMPA), 50 parts of AC (acetone), 3.5 parts of triethylamines, 35 parts of deionized waters, 1 part of quadrol.
Embodiment seven: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of poly-diethylene glycol adipates, 3 parts of ethylene glycol, 1 part of TriMethylolPropane(TMP), 40 parts of many aziridine, 0.2 part of organic bismuth catalyst, 2,6 parts of 2-dimethylol propionic acids (DMPA), 60 parts of AC (acetone), 4 parts of triethylamines, 35 parts of deionized waters, 1.5 parts of diethylenetriamines.
Embodiment eight: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 100 parts of poly adipate succinic acid esters, 3 parts of glycol ethers, 2 parts of TriMethylolPropane(TMP)s, 55 parts, aminoresin, 0.2 part of organic bismuth catalyst, 2,4 parts of 2-dimethylol propionic acids (DMPA), 80 parts of AC (acetone), 3.5 parts of triethylamines, 35 parts of deionized waters, 1.5 parts of quadrols.
Embodiment nine: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 80 parts of poly-hexanodioic acid hexylene glycol esters, 20 parts of polypropylene glycols, 3 parts of glycol ethers, 1.5 parts of TriMethylolPropane(TMP)s, 20 parts of tolylene diisocyanates (TDI), 35 parts of isophorone diisocyanates (IPDI), 0.2 part of organic bismuth catalyst, 2,5 parts of 2-dimethylol propionic acids (DMPA), 80 parts of AC (acetone), 4 parts of triethylamines, 35 parts of deionized waters, 1 part of quadrol.
Embodiment ten: a kind of aqueous polyurethane patch glue, by weight, its technical recipe is as follows: 70 parts of poly adipate succinic acid esters, 30 parts of polypropylene glycols, 1,42 parts of butyleneglycols, 1.5 parts of TriMethylolPropane(TMP)s, 20 parts of tolylene diisocyanates (TDI), 35 parts of isophorone diisocyanates (IPDI), 0.15 part of organic bismuth catalyst, 5 parts of 2,2-dimethylol propionic acids (DMPA), 100 parts of AC (acetone), 3.5 parts of triethylamines, 35 parts of deionized waters, 2 parts of quadrols.
Claims (9)
1. an aqueous polyurethane patch glue, is characterized in that: by weight, its technical recipe is as follows: 100 parts of macromolecular polyols, 1～3 part of small molecule chain extender, 1～3 part of small molecules linking agent, waterborne curing agent 30-80 part, 0.1～0.2 part of organic bismuth catalyst, 2,3～8 parts of 2-dimethylol propionic acids, 50～100 parts, acetone, 2～6 parts of triethylamines, 30～40 parts of deionized waters, 0.5～1.5 part of polyamine.
2. a kind of aqueous polyurethane patch glue according to claim 1, is characterized in that: described macromolecular polyol is polyester polyethers, or their mixture.
3. a kind of aqueous polyurethane patch glue according to claim 2, is characterized in that: described polyester is polyethylene glycol adipate, poly-diethylene glycol adipate, poly adipate succinic acid ester, or poly-hexanodioic acid hexylene glycol ester; Described polyethers is polypropylene glycol.
4. a kind of aqueous polyurethane patch glue according to claim 1, is characterized in that: described small molecule chain extender is ethylene glycol glycol ether, or Isosorbide-5-Nitrae butyleneglycol.
5. a kind of aqueous polyurethane patch glue according to claim 1, is characterized in that: described small molecules linking agent is TriMethylolPropane(TMP).
6. a kind of aqueous polyurethane patch glue according to claim 1, is characterized in that: described waterborne curing agent is polyisocyanates, many aziridine, or aminoresin.
7. a kind of aqueous polyurethane patch glue according to claim 6, is characterized in that: the preferred tolylene diisocyanate of described polyisocyanates, isophorone diisocyanate; 20～50 parts of tolylene diisocyanates, 10～30 parts of isophorone diisocyanates.
8. a kind of aqueous polyurethane patch glue according to claim 1, is characterized in that: described polyamine is quadrol, or diethylenetriamine.
9. an aqueous polyurethane patch glue preparation method, is characterized in that: being equipped with in the reactor of mechanical stirrer, thermometer, reflux exchanger, add macromolecular polyol, and at 100 ℃-120 ℃, 1hr dewaters under the condition of vacuum≤-0.8MPa, under 80 ℃ of conditions, add small molecule chain extender and the small molecules linking agent of metering, waterborne curing agent, organic bismuth catalyst is appropriate, reaction 3hr, NCO content in detection system, in the time that NCO content reaches theoretical value, be cooled to 60 ℃, add with 2 of N-Methyl pyrrolidone dissolving, 2-dimethylol propionic acid, and react 4-5hr at this temperature, survey NCO content adds acetone viscosity reduction while reaching theoretical value, obtain the performed polymer of NCO end-blocking, be cooled to≤add triethylamine after 50 ℃, after neutralization reaction number minute, under stirring, high speed dispersion adds the deionized water emulsification measuring, after add polyamine chain extension, vacuum decompression is sloughed acetone, make solid content and be 35% blue light emulsion aqueous polyurethane patch glue.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104073213A (en) * | 2014-06-26 | 2014-10-01 | 安徽神舟飞船胶业有限公司 | Formula and preparation process of aqueous polyurethane adhesive |
| CN104312521A (en) * | 2014-11-14 | 2015-01-28 | 成都市和乐门业有限公司 | Single component low-temperature polyurethane foaming adhesive and preparation method thereof |
| CN105754536A (en) * | 2016-03-10 | 2016-07-13 | 张家港锐码新材料有限公司 | Transparent antistatic pressure-sensitive adhesive |
| CN105860010A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Preparing method for solvent-free polyurethane adhesive for fabric-fabric combination |
| CN105860011A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Cloth compositing method based on solvent-free polyurethane adhesive |
| CN109735289A (en) * | 2018-12-26 | 2019-05-10 | 深圳日高胶带新材料有限公司 | A kind of polymer composite gluing agent prescription and its manufacture craft |
| CN112266460A (en) * | 2020-11-06 | 2021-01-26 | 安徽聚合辐化化工有限公司 | Thermosetting polyurethane and preparation method thereof |
| CN113249080A (en) * | 2021-05-11 | 2021-08-13 | 广州慧谷化学有限公司 | Water-dispersible hot melt adhesive and preparation method thereof |
| CN113549421A (en) * | 2021-07-13 | 2021-10-26 | 温州市大宝高分子材料有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073213A (en) * | 2014-06-26 | 2014-10-01 | 安徽神舟飞船胶业有限公司 | Formula and preparation process of aqueous polyurethane adhesive |
| CN104312521A (en) * | 2014-11-14 | 2015-01-28 | 成都市和乐门业有限公司 | Single component low-temperature polyurethane foaming adhesive and preparation method thereof |
| CN104312521B (en) * | 2014-11-14 | 2016-08-17 | 成都市和乐门业有限公司 | Single-component low temperature polyurethane foam glue and preparation method thereof |
| CN105754536A (en) * | 2016-03-10 | 2016-07-13 | 张家港锐码新材料有限公司 | Transparent antistatic pressure-sensitive adhesive |
| CN105860010A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Preparing method for solvent-free polyurethane adhesive for fabric-fabric combination |
| CN105860011A (en) * | 2016-06-08 | 2016-08-17 | 江苏华大新材料有限公司 | Cloth compositing method based on solvent-free polyurethane adhesive |
| CN109735289A (en) * | 2018-12-26 | 2019-05-10 | 深圳日高胶带新材料有限公司 | A kind of polymer composite gluing agent prescription and its manufacture craft |
| CN112266460A (en) * | 2020-11-06 | 2021-01-26 | 安徽聚合辐化化工有限公司 | Thermosetting polyurethane and preparation method thereof |
| CN113249080A (en) * | 2021-05-11 | 2021-08-13 | 广州慧谷化学有限公司 | Water-dispersible hot melt adhesive and preparation method thereof |
| CN113549421A (en) * | 2021-07-13 | 2021-10-26 | 温州市大宝高分子材料有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
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