CN104448219A - Aqueous polyurethane resin for pressure-sensitive adhesive and preparation method thereof - Google Patents
Aqueous polyurethane resin for pressure-sensitive adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN104448219A CN104448219A CN201310418933.8A CN201310418933A CN104448219A CN 104448219 A CN104448219 A CN 104448219A CN 201310418933 A CN201310418933 A CN 201310418933A CN 104448219 A CN104448219 A CN 104448219A
- Authority
- CN
- China
- Prior art keywords
- sensitive adhesive
- polyurethane resin
- 120min
- pressure sensitive
- emulsification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses aqueous polyurethane resin for a pressure-sensitive adhesive and a preparation method thereof. The preparation method comprises the following steps of carrying out pressure reduction dehydration on hydroxyl-terminated polyester polyol, carrying out cooling, adding diisocyanate into a reactor, carrying out a reaction process at a temperature of 70-90 DEG C for 110-120min, adding a dimethylolpropionic acid solution into the reaction product, carrying out a reaction process for 110-120min, cooling the reaction product to 50-55 DEG C, adding triethylamine into the reaction product for neutralization, carrying out full stirring for 8-10min, stopping stirring, fast pouring deionized water into the reactor, starting stirring and emulsification devices, carrying out emulsification for 8-10min, adding an ethanediamine solution into the emulsion, sequentially carrying out emulsification for 8-10min, stopping emulsification, sequentially carrying out stirring for 90-120min, carrying out filtration and discharging the product. The aqueous polyurethane resin has 180 degree peel strength of 30-300g/25mm. Through coating machine-based coating, a plurality of the pressure-sensitive adhesive products with excellent performances are obtained and can be widely used for all industries. The preparation method is simple and easy.
Description
Technical field
The present invention relates to a kind of waterborne polyurethane pressure-sensitive adhesives, particularly be a kind of waterborne polyurethane resin for pressure sensitive adhesive and preparation method thereof.
Background technology
The full name of pressure sensitive adhesive is pressure-sensitive sizing agent, is commonly called as non-setting adhesive, is the class in sizing agent system.Pressure-sensitive adhesive agent can be divided into according to curing mode and proterties: solvent pressure-sensitive adhesive, emulsion-type pressure-sensitive, water-soluble pressure sensitive adhesive, thermotropic pressure sensitive glue, ultraviolet curing type pressure sensitive adhesive, electron(beam)curing type pressure sensitive adhesive etc.Pressure-sensitive adhesive agent can be divided into again according to the constituent structure of matrix resin: rubber-like pressure sensitive adhesive, polyacrylate(s) pressure sensitive adhesive, polyvingl ether resene, polyurethanes, polyisobutene class etc.
Pressure sensitive adhesive originates from Later Han Dynasty's period of B.C. 1600 China, and in " herbal medicine addendum Huang di's Canon of Medicine ", recite the plaster that treatment is grieved, it is the pressure sensitive adhesive blank boiled with herbal medicine and rosin, gelatin.Until 18th century ancient Egypt just occur that the plaster that rosin, beeswax etc. make is applied in medical treatment; 1870, after plaster class material made by u s company's rubber and resin, 1882, German pharmacist made zinc oxide adhesive plaster, from then on worldwide entered the suitability for industrialized production epoch of pressure-sensitive tape.
In numerous pressure sensitive adhesives, natural rubber pressure sensitive sizing agent develops the earliest, and still occupy a class pressure sensitive adhesive of critical role so far.Although the agent of various synthetic rubber pressure-sensitive adhesive is important not as natural rubber pressure sensitive glue, because kind is a lot of and differ from one another, therefore also there is certain status in pressure sensitive adhesive field.Rubber pressure-sensitive adhesive mostly is solvent based product, and solvent mostly is gasoline, normal hexane, pentane and aromatic hydrocarbon solvent as toluene etc., inflammable and poisonous and harmful, and system viscosity is very large, is not suitable for high density coating; Aqueous product is viscous force and 180 just
ostripping strength is all not so good as corresponding solvent pressure-sensitive adhesive.
Acrylic ester polymer is just widely used as pressure-sensitive adhesive agent in the 1950's, and until just occupies critical role in pressure sensitive adhesive field the sixties.China is the research and development being devoted to polyacrylate pressure-sensitive from 20 century 70s mid-term, from initial solvent-borne type, is transitioned into present emulsion-type, may be used for most of protective membrane product at present.Its major advantage is:
cost is low, safety, nuisanceless;
processing ease during polymer polymerizing, polymerization time is short;
polymericular weight is higher;
easily make the pressure-sensitive adhesive agent of high density, low-viscosity.Its shortcoming is water tolerance, poor electrical performance, and rate of drying is slow, and energy expenditure is large, and surface tension is high, and coating performance, not as good as solvent type polyacrylate pressure sensitive adhesive, some base material can produce glue, thus causes serious quality problems.
Waterborne polyurethane pressure-sensitive adhesives sticks agent and has all advantages that polyacrylate pressure-sensitive sticks agent, has excellent heat-resisting cold tolerance simultaneously; Adopt self-emulsification in preparation process, not containing emulsifying agent, there is excellent water tolerance; Molecular weight distribution is relatively more even, and being not easy glue, without ghost, is the very promising pressure-sensitive adhesive agent of one.
Chinese invention patent application prospectus publication number CN1456630 provides one " hydrophilic polyurethane pressure-sensitive adhesive and preparation method thereof "; The hydrophilic polyurethane pressure-sensitive adhesive water tolerance that this specification sheets provides is not good; (a kind of protective membrane nano-modification waterborne polyurethane pressure-sensitive adhesive and preparation method thereof) that Chinese invention patent application prospectus publication number CN103031103A provides, the deficiency of existence needs to add nano modification ion to improve the performance of sizing agent.
Summary of the invention
The object of the present invention is to provide and be a kind ofly suitable for that multiple base material, stripping strength are stablized, heat-resisting cold-resistant, water tolerance better, be not easy glue, the waterborne polyurethane resin for pressure sensitive adhesive without ghost.
The object of the present invention is to provide is the preparation method of the above-mentioned waterborne polyurethane resin for pressure sensitive adhesive.
The waterborne polyurethane resin that the present invention is used for pressure sensitive adhesive comprises following component:
Hydroxyl telechelic polyester polyvalent alcohol: x weight part;
Vulcabond: 0.167x ~ 0.262x weight part
Dimethylol propionic acid: 0.05x ~ 0.06x weight part;
Triethylamine: 0.034x ~ 0.043x weight part;
Quadrol: 0.002x ~ 0.0063x weight part;
Deionized water: hydroxyl telechelic polyester polyvalent alcohol, vulcabond, dimethylol propionic acid and quadrol quality summation 1.4 times;
Hydroxyl telechelic polyester polyvalent alcohol of the present invention is the multipolymer of phthalic anhydride, 1,6-hexanodioic acid, neopentyl glycol, ethylene glycol, and wherein the ratio of the amount of substance of phthalic anhydride and 1,6-hexanodioic acid is 3 ︰ 2, and the ratio of the amount of substance of neopentyl glycol and ethylene glycol is 4 ︰ 3.
The hydroxy radical content of hydroxyl telechelic polyester polyvalent alcohol of the present invention is 0.8 ~ 1.0mmol/g.
Vulcabond of the present invention is TDI-80, or TDI-80 and the mixture both liquefied mdi.
Dimethylol propionic acid solution of the present invention is the N-Methyl pyrrolidone solution of dimethylol propionic acid obtained after dimethylol propionic acid solvent N-methyl pyrilidone dissolves, wherein, and dimethylol propionic acid: N-Methyl pyrrolidone weight ratio=3:7.
Ethylenediamine solution of the present invention is the aqueous solution of quadrol obtained after quadrol dilute with water, wherein, and quadrol: water weight ratio=5:95.
Preparation method of the present invention comprises the following steps: first by hydroxyl telechelic polyester polyvalent alcohol decompression dehydration, be cooled to 60 ~ 70 after dehydration
dEG C, then the vulcabond of 0.167 ~ 0.262 of hydroxyl telechelic polyester polyol quality times is added reactor, 75 ~ 85
dEG Creaction 110 ~ 120min, adds the dimethylol propionic acid solution of 0.167 ~ 0.2 times of hydroxyl telechelic polyester polyol quality subsequently, continues 75 ~ 85
dEG Creaction 110 ~ 120min;
treat step
after reaction terminates, material is cooled to 50 ~ 55
dEG C,add the triethylamine of 0.034 ~ 0.043 times of hydroxyl telechelic polyester polyol quality, stir 8 ~ 10min, deionized water is injected toward reactor, drive stirring and mulser, emulsification 8 ~ 10min, then adds the ethylenediamine solution of 0.04 ~ 0.126 times of hydroxyl telechelic polyester polyol quality, continue emulsification 8 ~ 10min, stop emulsification, continue stirring 90 ~ 120min, filter discharging.This reactant is the waterborne polyurethane resin for pressure sensitive adhesive.
Step of the present invention
in, the decompression dehydration of hydroxyl telechelic polyester polyvalent alcohol is: hydroxyl telechelic polyester polyvalent alcohol is dropped into reactor and is heated to 100-~ 120
dEG C, be decompressed to below vacuum tightness 5Kpa and dewater, dewatering time controls at 90 ~ 120min.
The present invention by hydroxyl telechelic polyester polyvalent alcohol decompression dehydration, then generated isocyanate terminated performed polymer with isocyanate reaction before this, then reacted with dimethylol propionic acid, generated the performed polymer containing carboxyl terminal isocyanic ester; Add triethylamine neutralization, then add water and carry out emulsify at a high speed, finally add quadrol and carry out chain extension, obtained waterborne polyurethane resin, this resin is good to substrate bonding, and stripping strength is stablized, and can be used for pressure-sensitive adhesive agent.
The hydroxyl telechelic polyester polyvalent alcohol that the present invention is prepared with phthalic anhydride, 1,6-hexanodioic acid, neopentyl glycol and ethylene glycol is first for raw material, and obtained water-fast good, heat-resisting cold-resistant, that stripping strength is stable waterborne polyurethane pressure-sensitive adhesives sticks agent, for pressure sensitive adhesive, and 180
ostripping strength (GB 2792-81) 30 ~ 300g/25mm; Can single component directly use; Through coating machine coating, the multiple pressure sensitive adhesive goods of excellent property can be obtained, be widely used in industry-by-industry.Preparation method of the present invention is simple, and raw material is easy to get, and technique can be handling good, constant product quality.
Embodiment
The polyvalent alcohol of hydroxyl telechelic polyester described in following examples is the multipolymer of phthalic anhydride, 1,6-hexanodioic acid, neopentyl glycol, ethylene glycol, and wherein the ratio of the amount of substance of phthalic anhydride and 1,6-hexanodioic acid is 3 ︰ 2, and the ratio of the amount of substance of neopentyl glycol and ethylene glycol is 4 ︰ 3; The hydroxy radical content of hydroxyl telechelic polyester polyvalent alcohol is 0.8 ~ 1.0mmol/g; Dimethylol propionic acid in the N-Methyl pyrrolidone solution of described dimethylol propionic acid: the weight ratio=3:7 of N-Methyl pyrrolidone; Quadrol in ethylenediamine solution: the weight ratio=5:95 of water.
Embodiment 1:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 100.22kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 100 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 21.48Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1055Kg toward reactor, drive stirring and mulser, add 47.08Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 300g.
Embodiment 2:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 100.22kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 110 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 22.38Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1028Kg toward reactor, drive stirring and mulser, add 34.45Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 270g.
Embodiment 3:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 100.22kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 120 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 23.06Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1032Kg toward reactor, drive stirring and mulser, add 24.24Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 240g.
Embodiment 4:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 87kgTDI, 25Kg liquefied mdi, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 110 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 22.38Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1076Kg toward reactor, drive stirring and mulser, add 47.77Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 200g.
Embodiment 5:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 69.6kgTDI, 50Kg liquefied mdi, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 116 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 23.08Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1058Kg toward reactor, drive stirring and mulser, add 38.51Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 220g.
Embodiment 6:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.8mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 52.2kgTDI, 75Kg liquefied mdi, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 120 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 23.06Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1070Kg toward reactor, drive stirring and mulser, add 32.88Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 210g.
Embodiment 7:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.9mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 112.75kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 100 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 21.48Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1044Kg toward reactor, drive stirring and mulser, add 64.72Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 150g.
Embodiment 8:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.9mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 112.75kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 110 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 22.38Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1047Kg toward reactor, drive stirring and mulser, add 50.58Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 120g.
Embodiment 9:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.9mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 65.25kgTDI, 75Kg liquefied mdi, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 110 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 23.62Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1087Kg toward reactor, drive stirring and mulser, add 66.67Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 100g.
Embodiment 10:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 0.9mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 56.55kgTDI, 87.5Kg liquefied mdi, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 120 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 25.78Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1095Kg toward reactor, drive stirring and mulser, add 52.36Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 50g.
Embodiment 11:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 1.0mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 125.28kgTDI, at 80 DEG C of insulation 110 ~ 120min, adds the N-Methyl pyrrolidone solution of 100 kg dimethylol propionic acids, continues, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 20.35Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1062Kg toward reactor, drive stirring and mulser, add 75.31Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 90g.
Embodiment 12:
Be the hydroxyl telechelic polyester polyvalent alcohol input reactor of 1.0mmol/g by 600Kg hydroxy radical content, be warming up to 100 ~ 120
dEG C, decompression dehydration 120 minutes, is cooled to 60 ~ 70 DEG C and adds 69.6kgTDI, 87.5 liquefied mdis, at 80 DEG C of insulation 110 ~ 120min, add the N-Methyl pyrrolidone solution of 120 kg dimethylol propionic acids, continue, at 80 DEG C of insulation 110 ~ 120min, to be cooled to 50 ~ 55
dEG C,add 25.78Kg triethylamine, abundant stirring 10min, stops stirring, injects rapidly the deionized water of 1114Kg toward reactor, drive stirring and mulser, add 65.28Kg ethylenediamine solution after emulsification 10min, continue emulsification 10min, stop emulsification, continue to stir 120min, filter discharging, plastic tank packaging, this reactant is the waterborne polyurethane resin for pressure sensitive adhesive, and 180
ostripping strength 30g.
Claims (8)
1., for a waterborne polyurethane resin for pressure sensitive adhesive, it is characterized in that comprising following component:
Hydroxyl telechelic polyester polyvalent alcohol: x weight part;
Vulcabond: 0.167x ~ 0.262x weight part
Dimethylol propionic acid solution: 0.167x ~ 0.20x weight part;
Triethylamine: 0.034x ~ 0.043x weight part;
Ethylenediamine solution: 0.04x ~ 0.126x weight part;
Deionized water: hydroxyl telechelic polyester polyvalent alcohol, vulcabond, dimethylol propionic acid solution and ethylenediamine solution quality summation 1.2 ~ 1.4 times.
2. according to claim 1 for the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that: described hydroxyl telechelic polyester polyvalent alcohol is phthalic anhydride, 1, the multipolymer of 6-hexanodioic acid, neopentyl glycol, ethylene glycol, wherein phthalic anhydride and 1, the ratio of the amount of substance of 6-hexanodioic acid is 3 ︰ 2, and the ratio of the amount of substance of neopentyl glycol and ethylene glycol is 4 ︰ 3.
3. according to claim 1 for the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that: the hydroxy radical content of described hydroxyl telechelic polyester polyvalent alcohol is 0.8 ~ 1.0mmol/g.
4. according to claim 1 for the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that: described vulcabond is TDI-80, or TDI-80 and the mixture both liquefied mdi.
5. according to claim 1 for the preparation method of the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that: described dimethylol propionic acid solution is obtained after dimethylol propionic acid solvent N-methyl pyrilidone dissolves, wherein, dimethylol propionic acid: N-Methyl pyrrolidone weight ratio=3:7.
6. according to claim 1 for the preparation method of the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that: described ethylenediamine solution is obtained after quadrol dilute with water, wherein, quadrol: water weight ratio=5:95.
7., for a preparation method for the waterborne polyurethane resin of pressure sensitive adhesive, the method comprises the following steps:
first by hydroxyl telechelic polyester polyvalent alcohol decompression dehydration, after dehydration, 60 ~ 70 are cooled to
dEG C, then the vulcabond of 0.167 ~ 0.262 of hydroxyl telechelic polyester polyol quality times is added reactor, 75 ~ 85
dEG Creaction 110 ~ 120min, adds the dimethylol propionic acid solution of 0.167 ~ 0.2 times of hydroxyl telechelic polyester polyol quality subsequently, continues 75 ~ 85
dEG Creaction 110 ~ 120min;
treat step
after reaction terminates, material is cooled to 50 ~ 55
dEG C,add the triethylamine of 0.034 ~ 0.043 times of hydroxyl telechelic polyester polyol quality, stir 8 ~ 10min, deionized water is injected toward reactor, drive stirring and mulser, emulsification 8 ~ 10min, then adds the ethylenediamine solution of 0.04 ~ 0.126 times of hydroxyl telechelic polyester polyol quality, continue emulsification 8 ~ 10min, stop emulsification, continue stirring 90 ~ 120min, filter discharging.
8., according to claim 7 for the preparation method of the waterborne polyurethane resin of pressure sensitive adhesive, it is characterized in that in step
in, the decompression dehydration of hydroxyl telechelic polyester polyvalent alcohol is: hydroxyl telechelic polyester polyvalent alcohol is dropped into reactor and is heated to 100-~ 120
dEG C, be decompressed to below vacuum tightness 5Kpa and dewater, dewatering time controls at 90 ~ 120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310418933.8A CN104448219B (en) | 2013-09-16 | 2013-09-16 | A kind of waterborne polyurethane resin for pressure sensitive adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310418933.8A CN104448219B (en) | 2013-09-16 | 2013-09-16 | A kind of waterborne polyurethane resin for pressure sensitive adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104448219A true CN104448219A (en) | 2015-03-25 |
| CN104448219B CN104448219B (en) | 2018-01-30 |
Family
ID=52895018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310418933.8A Active CN104448219B (en) | 2013-09-16 | 2013-09-16 | A kind of waterborne polyurethane resin for pressure sensitive adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448219B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049601A (en) * | 1974-02-19 | 1977-09-20 | Anchor Continental, Inc. | Moisture-resistant polyurethane-based pressure-sensitive adhesives |
| WO2001062818A1 (en) * | 2000-02-25 | 2001-08-30 | 3M Innovative Properties Company | Polyurethane-based adhesives, systems for such adhesives, articles therefrom, and methods of making |
| JP2002188072A (en) * | 2000-09-28 | 2002-07-05 | Sanyo Chem Ind Ltd | Polyurethane composition for forming adhesive for sticking plastic floor board |
| CN1456630A (en) * | 2003-03-14 | 2003-11-19 | 天津大学 | Hydrophilic polyurethane pressure-sensitive adhesive and preparing method thereof |
| CN101052663A (en) * | 2004-09-30 | 2007-10-10 | 旭硝子株式会社 | Method for producing urethane resin and pressure sensitive adhesive |
| CN102898969A (en) * | 2012-10-22 | 2013-01-30 | 东莞隽思印刷有限公司 | Water-washable non-setting adhesive and preparation method thereof |
| CN103031103A (en) * | 2012-12-27 | 2013-04-10 | 广东达美新材料有限公司 | Nano-modification waterborne polyurethane pressure-sensitive adhesive for protective film and preparation method of nano-modification waterborne polyurethane pressure-sensitive adhesive |
-
2013
- 2013-09-16 CN CN201310418933.8A patent/CN104448219B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049601A (en) * | 1974-02-19 | 1977-09-20 | Anchor Continental, Inc. | Moisture-resistant polyurethane-based pressure-sensitive adhesives |
| WO2001062818A1 (en) * | 2000-02-25 | 2001-08-30 | 3M Innovative Properties Company | Polyurethane-based adhesives, systems for such adhesives, articles therefrom, and methods of making |
| JP2002188072A (en) * | 2000-09-28 | 2002-07-05 | Sanyo Chem Ind Ltd | Polyurethane composition for forming adhesive for sticking plastic floor board |
| CN1456630A (en) * | 2003-03-14 | 2003-11-19 | 天津大学 | Hydrophilic polyurethane pressure-sensitive adhesive and preparing method thereof |
| CN101052663A (en) * | 2004-09-30 | 2007-10-10 | 旭硝子株式会社 | Method for producing urethane resin and pressure sensitive adhesive |
| CN102898969A (en) * | 2012-10-22 | 2013-01-30 | 东莞隽思印刷有限公司 | Water-washable non-setting adhesive and preparation method thereof |
| CN103031103A (en) * | 2012-12-27 | 2013-04-10 | 广东达美新材料有限公司 | Nano-modification waterborne polyurethane pressure-sensitive adhesive for protective film and preparation method of nano-modification waterborne polyurethane pressure-sensitive adhesive |
Non-Patent Citations (4)
| Title |
|---|
| 刘益军，: "《聚氨酯原料及助剂手册》", 31 January 2013 * |
| 张立武，: "《水基胶粘剂》", 31 January 2002 * |
| 石鑫等，: ""水性聚氨酯压敏胶的制备与性能研究"", 《中国胶黏剂》 * |
| 黎兵，: ""水性聚氨酯压敏胶的合成及其性能表征"", 《中国胶黏剂》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104448219B (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107540883B (en) | Preparation method of carboxymethyl chitosan/graphene oxide/poly (N-isopropylacrylamide) nano composite hydrogel | |
| CN101735763B (en) | Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof | |
| CN103725231B (en) | Adhesive material for adhesive tapes and preparation method thereof | |
| CN109370127B (en) | Two-dimensional layered material-polyvinyl alcohol hydrogel and preparation method thereof | |
| CN103396753A (en) | Preparation method of hot-melt polyurethane resin for bonding material | |
| Zhu et al. | Thermally assisted self‐healing polyurethane containing carboxyl groups | |
| CN103045068B (en) | A kind of aluminium foil use coating-forming agent and preparation method thereof | |
| CN108728032A (en) | A kind of water-based polyurethane adhesive and preparation method thereof, the application in food plastic flexible package | |
| CN106854449A (en) | A kind of paper-plastic stick solvent-free single-component glue and preparation method thereof | |
| CN103087306A (en) | Amphipathy hyperbranched SIBS elastomer and preparation method and usage thereof | |
| CN112592418A (en) | Preparation method of polyvinyl alcohol special for optical film | |
| CN104845575A (en) | Cooking resistance type modified polyurethane adhesive preparation method | |
| CN104925865A (en) | New method for preparing molybdenum disulfide nanosheet by supercritical fluid auxiliary stripping | |
| CN104927746B (en) | A kind of moisture-curable polyurethane hot melt adhesive of long skinning time and preparation method thereof | |
| CN112063357A (en) | Solvent-free two-component polyurethane adhesive and preparation method and application thereof | |
| CN104448219A (en) | Aqueous polyurethane resin for pressure-sensitive adhesive and preparation method thereof | |
| TWI587761B (en) | Adhesive composition, film-like adhesive, adhesive sheet, circuit-connected body, method for connecting circuit component, use of adhesive composition, use of film-like adhesive and use of adhesive sheet | |
| Zhou et al. | Intrinsically self-healing and stretchy poly (urethane-urea) elastomer based on dynamic urea bonds and thiol-ene click reaction | |
| CN109796895A (en) | Degradable adhesive tape and preparation method thereof | |
| CN107286885A (en) | A kind of different direction conductive adhesive film and preparation method thereof | |
| CN107936906A (en) | A kind of OLED Protection glues and preparation method thereof | |
| CN104974313A (en) | Preparation method of waterborne polyurethane based on glycidyl methacrylate | |
| TWI498065B (en) | Anisotropic conductive film and semiconductor device | |
| CN103709689B (en) | The preparation method of the homodisperse PET film of a kind of vanadium dioxide | |
| Polloni et al. | Ultrasound assisted miniemulsion polymerization to prepare poly (urea-urethane) nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 7 Tianyu Avenue, Xiangcheng High tech Development Zone, Xiangcheng District, Xiangyang City, Hubei Province, 441000 Patentee after: Hubei Aerospace Chemical New Materials Technology Co.,Ltd. Address before: No. 58, Qinghe Road, box 156, Xiangfan City, Hubei Province, 441003 Patentee before: XIANGYANG SUNVAIOR AEROSPACE FILMS Co.,Ltd. |
|
| CP03 | Change of name, title or address |