CN103435760A - Method for preparing modified double-component high-temperature-resistant waterborne polyurethane pressure-sensitive adhesive - Google Patents
Method for preparing modified double-component high-temperature-resistant waterborne polyurethane pressure-sensitive adhesive Download PDFInfo
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Abstract
The invention discloses a method for preparing a modified double-component high-temperature-resistant waterborne polyurethane pressure-sensitive adhesive. The method comprises the following steps: adding polyisocyanate and low polymer polyhydric alcohol into reaction equipment, further adding a hydrophilic chain extender to react to obtain a polyurethane prepolymer, subsequently adding acrylic ester containing hydroxyl and a modified epoxy resin so as to obtain the modified polyurethane prepolymer; further adding a neutralizer to neutralize, adding water, subsequently dispersing by using a high-speed dispersing machine so as to obtain a modified waterborne polyurethane dispersoid; uniformly dripping acrylate monomer, a modified rosin resin and an initiating agent so as to obtain a modified waterborne polyurethane dispersoid; further adding a defoaming agent, and finally adding a curing agent additionally so as to obtain the modified double-component high-temperature-resistant waterborne polyurethane pressure-sensitive adhesive. The pressure-sensitive adhesive prepared through the method is high in primary adhesion property, release force, adhesion lasting property and high-temperature adhesion lasting property; a high-temperature-resistant pressure-sensitive adhesive tape prepared from the adhesive can meet the requirements of automobile and electronic industries. According to the invention, the preparation process is simple, the production period is short and the operation cost is low.
Description
Technical field
The present invention relates to can be used for the preparation method of a kind of high temperature resistant pressure sensitive adhesive in the fields such as automobile, electronic industry, be specifically related to a kind of preparation method of modified double components aqueous polyurethane high temperature resistant pressure sensitive adhesive.
Background technology
Along with high-tech development, the pressure sensitive adhesive high performance has become the focus of high performance pressure sensitive adhesive tapes and label.There is high performance pressure sensitive adhesive tapes and the label that high performance pressure sensitive adhesive makes and be widely used in the fields such as automobile, electronic apparatus, wind power generation plant, aviation; tied up, covered, sealing, protection, splicing, press back, fixing, sign, anticorrosion etc., its demand growth is rapid.Along with the development in field and improving constantly of performance requriements thereof such as automobile, electronic apparatus, wind power generation plant, aviations, the important subsidiary material of a class that Pressuresensitive Tape and label are essential as this field, its application is more and more extensive.Pressuresensitive Tape and label, as a kind of manufactured consumer goods, are used in a large number in all trades and professions.Common Pressuresensitive Tape and label technique are very ripe in China's Mainland, drug on the market for its output, yet the Pressuresensitive Tape of using in fields such as automobile, electron trades and labeling requirement high-peeling strength, height are held viscous force and high initial bonding strength, strict to adaptability heat-resisting, severe environment.
High performance pressure sensitive adhesive tapes and the label for fields such as automobile, electronic industries, used are at home at present used solvent pressure-sensitive adhesive mostly, and these Pressuresensitive Tapes and label are owing to using solvent pressure-sensitive adhesive, solvent pressure-sensitive adhesive is owing to containing a large amount of volatile organic compoundss (VOC), and environmental pollution is serious.The cry of public opinion of preserving the ecological environment grows with each passing day, and some developed countries have formulated fire codes and solvent rules in succession, have limited the use of solvent-based adhesive.Enhancing along with day by day sound and people's environmental consciousness of Environmental Protection in China rules, the environmental-protection type adhesive that quality is good, pollution-free, integrate with international standard will replace solvent-borne type, become the main product of synthetic adhesive, therefore developing environment-friendly type high performance Pressuresensitive Tape and label is the trend of adhesives industries development both at home and abroad with pressure sensitive adhesive.
At present, in China's water-base cement pressure sensitive sticking agent, or take acrylate resin glue etc. as main.Acrylic resin pressure sensitive adhesive pressure-sensitive is good, yet the low temperature resistant and high thermal resistance of this pressure sensitive adhesive glue is not good.Water-based polyurethane adhesive, be called for short water-based PU tackiness agent, it has that resistance to low temperature is good, bonding strength is higher, snappiness good, do not fire, nontoxic, free from environmental pollution, save the advantage such as the energy, and its viscosity does not have notable difference with the change of polymericular weight, can be by molecular-weight adjusting to desirable higher level, improve its cohesive strength, there is vast potential for future development.
Yet single aqueous polyurethane adhesive performance can't meet the needs of high-performance pressure sensitive adhesive, be mainly manifested in that pressure-sensitive is not good, rate of drying is slow, high thermal resistance is poor, can not meet domestic market far away to the growing demand of this high-quality environment protective type tackiness agent.Therefore how improving its pressure-sensitive, improve its high thermal resistance, accelerate its rate of drying, make its variety series, in order to be applicable to multi-purpose needs, is the problem that current scholar's research polyurethane adhesive will solve.
Summary of the invention
The object of the invention is to work out a kind of preparation method of aqueous polyurethane high temperature resistant pressure sensitive adhesive of modification, pressure sensitive adhesive initial bonding strength, the peeling force that this preparation method makes, holding viscous force and high temperature, to hold viscous force high, and the high temperature resistant pressure sensitive adhesive band of making can meet the needs of automobile, electronic industry.This patent preparation technology is simple, with short production cycle, and process cost is low, is easy to promotion and application.
The present invention adopts " molecule compounding technology " by modified epoxy (or epoxy soybean oil), acrylate and and modified rosin resin introduce waterborne polyurethane modified in, utilize polyurethane aqueous dispersion body as macromolecule emulsifier and reactant, via grafting and letex polymerization, make urethane and modified epoxy (or epoxy soybean oil), between acrylate and modified rosin, chemical bonding occurs, formation has the water-based composite emulsion of the modification of nucleocapsid structure and inierpeneirating network structure, then add defoamer, add again solidifying agent, obtain a kind of high temperature resistant pair of component pressure sensitive adhesive, can improve widely the pressure-sensitive of water-borne pressure sensitive adhesive, thermotolerance and chemical resistance.This pressure sensitive adhesive is usingd water as solvent, is conducive to environmental protection, and its excellent performance, have vast potential for future development in fields such as automobile, electronic industries.For improving the pressure-sensitive of polyurethane adhesive, improve its high thermal resistance, accelerate its rate of drying, enlarge the Application Areas of aqueous polyurethane, need carry out modification to urethane.Modified epoxy (or epoxy soybean oil) has the advantages such as chemical resistance is good, can participate in the reaction of aqueous polyurethane directly, forms reticulated structure, will improve Water-resistance of Waterborne Polyurethane and solvent resistance etc.Acrylic resin has that pressure-sensitive is good, ageing resistance and the advantage such as adhesiveproperties is good.Modified rosin resin not only cost is low, and can improve initial bonding strength and the peeling force of pressure sensitive adhesive after adding.
For achieving the above object, the present invention has taked following technical scheme:
A kind of preparation method of high-temperature resistant waterborne polyurethane pressure sensitive adhesive of modification, comprise the steps:
(1) preparation of base polyurethane prepolymer for use as: add polyisocyanates and oligomer polyol in conversion unit, react 2～3h under 60～80 ℃, then add wetting ability chainextender reaction 2～5h, obtain base polyurethane prepolymer for use as, wherein, the ratio of polyisocyanates and oligomer polyol amount of substance is 2.5～1.2:1; The mass ratio of polyisocyanates and chainextender is 10:0.5～1.5; Described oligomer polyol is polyester polyol or polyether glycol; Or described oligomer polyol is polybutadiene diol; Described wetting ability chainextender is dihydroxymethyl acetic acid, dimethylol propionic acid or dimethylolpropionic acid;
(2) base polyurethane prepolymer for use as of modification is synthetic: under 60～80 ℃, the acrylate of hydroxyl and modified epoxy are added in the base polyurethane prepolymer for use as that step (1) obtains and react 3～5h, then be cooled to 30-40 ℃, add in neutralizing agent and 10～20min, obtain the base polyurethane prepolymer for use as of modification, wherein, the mass ratio of the acrylate of polyisocyanates, hydroxyl, modified epoxy and neutralizing agent is 10:1～1.5:0.5～1:0.2～0.6; Synthesizing of described modified epoxy: epoxy resin is added in conversion unit, then add properties-correcting agent, under 120～150 ℃, react 2～3h, obtain the epoxy resin of modification; The properties-correcting agent addition is 1～10% of epoxy resin quality; Described properties-correcting agent is phosphoric acid or acetic acid;
(3) aqueous polyurethane dispersion is synthetic: in the modified polyurethane prepolymer after the neutralization obtained to step (2), add water, with high speed dispersor speed dispersion and emulsion 10～30min with 3000～5500rpm/min under 35 ℃～40 ℃, obtain aqueous polyurethane dispersion, the quality of described water is 40～45% for making this aqueous polyurethane dispersion solid content;
(4) preparation of the aqueous polyurethane dispersion of modification: in described aqueous polyurethane dispersion, evenly drip acrylate monomer, modified rosin resin and initiator, 70～75 ℃ of reaction 3～4h, then be warming up to 80～90 ℃, reaction 1～1.5h, lower the temperature again, discharging filter, obtain modified aqueous polyurethane dispersoid; The solid ingredient of described acrylate monomer, modified rosin resin, aqueous polyurethane dispersion and the mass ratio of initiator are 10～20:5～10:100:0.1～0.3; Described initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or benzoyl peroxide; The preparation of described modified rosin resin: rosin and Resorcinol are added in conversion unit, while being warmed up to 220 ℃-240 ℃, drip vinylformic acid, insulation, cool the temperature to 145-155 ℃ of discharging; Rosin, Resorcinol and acrylic acid mass ratio are 100:1～3:1～8;
(5) preparation of the aqueous polyurethane high temperature resistant pressure sensitive adhesive of modification: in described modified aqueous polyurethane dispersoid, add defoamer, obtain multiple modified aqueous polyurethane dispersion, external reinforcement agent again, obtain the double-component waterborne polyurethane pressure sensitive adhesive of heat resist modification; The mass ratio of described solidifying agent, modified aqueous polyurethane dispersoid and defoamer is 0.5～1:100:0.1～0.5; Described defoamer is the silicone oil defoamer; Described solidifying agent is isocyanate curing agent.
For further realizing the object of the invention, preferably, the polyisocyanates of described step (1) is tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditan-4,4 ˊ-vulcabond, poly methylene poly phenyl poly isocyanate or xylylene diisocyanate.Described polyester polyol comprises polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-BDO esterdiol, glycol ether esterdiol, polycarbonate diol or polycaprolactone glycol.Described polyether glycol is polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.Described epoxy resin is epoxy resin E-16, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51.The acrylate of described hydroxyl is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 or Propylene glycol monoacrylate.The neutralizing agent of described step (2) is triethylamine or trolamine.Described acrylate monomer is ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer.Described defoamer is ATF-1, ATF-2, BYK-141 and BYK-065/066 defoamer.The isocyanate curing agent that described solidifying agent is N3200, N3300, N3400 or N3600.
With respect to prior art, the present invention has following advantage:
(1) design synthetic multiple modified double-component waterborne polyurethane high temperature resistant pressure sensitive adhesive by latex particle.Adopt self-emulsification to carry out letex polymerization, do not need to add emulsifying agent in polymerization process, eliminate the impact of low molecule emulsifying agent on the pressure-sensitive adhesive performance.
(2) adopt " molecule compounding technology " by modified epoxy, acrylate and and modified rosin resin introduce in the modification of aqueous polyurethane, utilize polyurethane aqueous dispersion body as macromolecule emulsifier and reactant, via graft copolymerization and letex polymerization, the epoxy resin that makes urethane and contain two keys, acrylate and chemical bonding occurs containing between modified rosin resin, form the water-based hybrid emulsions with nucleocapsid structure and inierpeneirating network structure.The pressure-sensitive of acrylate excellence and weathering resistance, the epoxy resin chemical resistant properties is good, the Gum Rosin cost is low, tack is good advantage and elastic polyurethane characteristics good, that mechanical property is excellent are combined, make synthetic pressure sensitive adhesive combine the advantage of acrylate, epoxy resin, urethane and Gum Rosin.Add defoamer in modified aqueous polyurethane dispersoid, obtain multiple modified aqueous polyurethane dispersion, external reinforcement agent in the most backward this dispersion, obtain the double-component waterborne polyurethane pressure sensitive adhesive of heat resist modification.This pressure sensitive adhesive thermotolerance, chemical resistant properties and water-tolerant, initial bonding strength, peeling force, holding viscous force and high temperature, to hold viscous force high, and the Pressuresensitive Tape of making can meet the needs of automobile and electronics industry high temperature resistant pressure sensitive adhesive band.
(3) the method is easy to operate, technique is simple, with short production cycle, be easy to promotion and application.
(4) waterborne polyurethane pressure-sensitive adhesives of the modification that prepared by the present invention, its performance is suitable with the performance of external similar water-borne pressure sensitive adhesive, and cost is more much lower than external product.
Embodiment
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and describes in detail.But the scope of protection of present invention is not limited to the scope that embodiment means.
In following embodiment, the initial bonding strength test is measured according to GB4852-2002; Holding the viscous force test measures according to GB4851-1998; 180 ° of peeling forces are measured according to GB2792-1995; High temperature is held the viscous force test and is measured according to the GB4851-1998 standard.
Embodiment 1
The polyoxypropyleneglycol that is 2000 by 100g MDI, 320g molecular weight, at 75 ℃ of reaction 3h, then adds the 15g dimethylol propionic acid, and reaction 2h obtains base polyurethane prepolymer for use as; E-44 epoxy resin by the 6g modification, the 10g Hydroxyethyl acrylate joins in this performed polymer, under 78 ℃ with prepolymer reaction 3h, obtain the base polyurethane prepolymer for use as of modification, then be cooled to 35 ℃, add in the 5g triethylamine and 15min, add the 498g deionized water under the 3000r/min rotating speed, disperse 10min, obtain modified aqueous polyurethane dispersoid.Evenly drip the 50g butyl acrylate in this modified aqueous polyurethane dispersoid, 27g modified rosin resin and 0.67g Ammonium Persulfate 98.5,75 ℃ of reaction 3.5h, be warming up to again 85 ℃ of insulation reaction 1 hour, be down to room temperature, discharging is also filtered, and obtains the aqueous polyurethane dispersion of modification.The preparation of modified rosin resin: rosin and Resorcinol are added to be had agitator, in the conversion unit of thermometer and condenser, begins slowly to heat up, when temperature of reaction is raised to 220 ℃, drip lentamente again vinylformic acid, after dripping, then insulation, cool the temperature to 150 ℃ of dischargings; Rosin, Resorcinol and acrylic acid mass ratio are 100:1:1.Rosin is selected the superfine rosin of acid number >=166 (mgKOH/g).Synthesizing of the E-44 epoxy resin of modification: E-44 epoxy resin is incorporated with in the conversion unit of agitator, thermometer and condenser, adds properties-correcting agent, under 120 ℃, react 3h, obtain the epoxy resin of modification; The properties-correcting agent addition is 5% of E-44 epoxy resin quality; Properties-correcting agent is phosphoric acid;
Get the aqueous polyurethane dispersion of the above-mentioned modification of 100g, in this dispersion, add 0.5g solidifying agent N3200,0.2g defoamer ATF-1, obtain the water-based polyurethane adhesive of modification.
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and describes in detail.But the scope of protection of present invention is not limited to the scope that embodiment means.
In these product performance and prior art, solvent-borne type product SA550 Performance Ratio is in Table 1.
Table 1
| Quality index | SA550 | The product of the present embodiment |
| Solid content, % | 45 | 45 |
| Initial bonding strength/(steel ball, number) | 27 | 28 |
| 180 ° of peeling forces, N/25mm | 15 | 15.9 |
| Room temperature is held viscous force, h | 60 | 75 |
| High temperature is held viscous force, min | 200 | 240 |
As shown in table 1, its initial bonding strength of the fire resistant water-based pressure sensitive adhesive of product prepared by the present embodiment, 180 ° of peeling forces, room temperatures are held viscous force and high temperature, and to hold the performances such as viscous force suitable with solvent-borne type product SA550, part index number surpasses the solvent-borne type product, the high-performance adhesive tape of making can meet the needs of automobile, electronics industry Pressuresensitive Tape, and preparation technology is simple, be easy to promotion and application.
Embodiment 2
The polyethylene glycol adipate glycol that is 1000 by 100g TDI, 478g molecular weight, at 70 ℃ of reaction 2.5h, then adds 10g dihydroxymethyl acetic acid, and reaction 3h obtains base polyurethane prepolymer for use as; The epoxy resin E-20 of 10g modification, 10g Propylene glycol monoacrylate are joined in this performed polymer, under 65 ℃ with prepolymer reaction 4h, obtain the base polyurethane prepolymer for use as of modified epoxy modification, then be cooled to 30 ℃, add in the 5g trolamine and 15min, add the 531g deionized water under the 4500r/min rotating speed, disperse 15min, obtain modified aqueous polyurethane dispersoid.Evenly drip the 77g ethyl propenoate in this modified aqueous polyurethane dispersoid, the Gum Rosin of 20g modification and 0.6g Potassium Persulphate, 70 ℃ of reaction 3h, be warming up to again 80 ℃ of insulation reaction 1 hour, be down to room temperature, discharging is also filtered, and obtains the aqueous polyurethane dispersion of modification.The preparation of modified rosin resin: rosin and Resorcinol are added to be had agitator, in the conversion unit of thermometer and condenser, begins slowly to heat up, when temperature of reaction is raised to 220 ℃, drip lentamente again vinylformic acid, after dripping, then insulation, cool the temperature to 145 ℃ of dischargings; Rosin, Resorcinol and acrylic acid mass ratio are 100:3:8.Rosin is selected the superfine rosin of acid number >=166 (mgKOH/g).The epoxy resin E-20's of modification is synthetic: epoxy resin E-20 is incorporated with in the conversion unit of agitator, thermometer and condenser, adds properties-correcting agent acetic acid, under 150 ℃, react 2h, obtain the epoxy resin E-20 of modification; The properties-correcting agent addition is epoxy resin E-20 quality 1%.
Get the aqueous polyurethane dispersion of the above-mentioned modification of 100g, in this dispersion, add 0.7g solidifying agent N3300,0.1g defoamer ATF-2, obtain the water-based polyurethane adhesive of modification.
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and describes in detail.But the scope of protection of present invention is not limited to the scope that embodiment means.
In these embodiment product performance and prior art, solvent-borne type product SA550 Performance Ratio is in Table 2.
Table 2
| Quality index | SA550 | The product of the present embodiment |
| Solid content/% | 45 | 47.6 |
| Initial bonding strength/(steel ball, number) | 27 | 28 |
| 180 ° of peeling force/N/25mm | 15 | 16.1 |
| Room temperature is held viscous force/h | 60 | 78 |
| High temperature is held viscous force/min | 200 | 246 |
As shown in table 2, its initial bonding strength of the fire resistant water-based pressure sensitive adhesive of product prepared by the present embodiment, 180 ° of peeling forces, room temperatures are held viscous force and high temperature, and to hold the performances such as viscous force suitable with solvent-borne type product SA550, part index number surpasses the solvent-borne type product, the high-performance adhesive tape of making can meet the needs of automobile, electronics industry Pressuresensitive Tape, and preparation technology is simple, be easy to promotion and application.
Embodiment 3
The poly-hexanodioic acid that is 3000 by 100g IPDI and 640g molecular weight-BDO esterdiol, at 80 ℃ of reaction 3h, then adds the 12g dimethylol propionic acid, and reaction 4h obtains base polyurethane prepolymer for use as; 9.5g is joined in this performed polymer containing modification E-51 epoxy resin, 14g Hydroxyethyl acrylate, under 70 ℃ with prepolymer reaction 5h, obtain the base polyurethane prepolymer for use as of modified epoxy modification, then be cooled to 38 ℃, add in the 6g trolamine and 12min, add the 454g deionized water under the 4000r/min rotating speed, disperse 10min, obtain modified aqueous polyurethane dispersoid.Evenly drip the 35g Isooctyl acrylate monomer in this modified aqueous polyurethane dispersoid, 20g modified rosin resin and 0.5g Diisopropyl azodicarboxylate, 72 ℃ of reaction 4h, be warming up to again 88 ℃ of insulation reaction 1 hour, be down to room temperature, discharging is also filtered, and obtains the aqueous polyurethane dispersion of modification.
Get the aqueous polyurethane dispersion of the above-mentioned modification of 100g, in this dispersion, add 0.9g solidifying agent N3400,0.2g defoamer BYK-141, obtain the water-based polyurethane adhesive of modification.The preparation of modified rosin resin: rosin and Resorcinol are added to be had agitator, in the conversion unit of thermometer and condenser, begins slowly to heat up, when temperature of reaction is raised to 220 ℃, drip lentamente again vinylformic acid, after dripping, then insulation, cool the temperature to 155 ℃ of dischargings; Rosin, Resorcinol and acrylic acid mass ratio are 100:2:6.Rosin is selected the superfine rosin of acid number >=166 (mgKOH/g).Synthesizing of modification E-51 epoxy resin: E-51 epoxy resin is incorporated with in the conversion unit of agitator, thermometer and condenser, adds properties-correcting agent phosphoric acid, under 130 ℃, reaction 2.5h, obtain modification E-51 epoxy resin; The properties-correcting agent addition is 10% of E-51 epoxy resin total amount;
In these embodiment product performance and prior art, solvent-borne type product SA550 Performance Ratio is in Table 3.As shown in table 3, shown in, its initial bonding strength of the fire resistant water-based pressure sensitive adhesive of product prepared by the present embodiment, 180 ° of peeling forces, room temperatures are held viscous force and high temperature, and to hold the performances such as viscous force suitable with solvent-borne type product SA550, part index number surpasses the solvent-borne type product, the high-performance adhesive tape of making can meet the needs of automobile, electronics industry Pressuresensitive Tape, and preparation technology is simple, be easy to promotion and application.
Table 3
| Quality index | SA550 | The product of the present embodiment |
| Solid content/% | 45 | 48.5 |
| Initial bonding strength/(steel ball, number) | 27 | 30 |
| 180 ° of peeling force/N/25mm | 15 | 16.4 |
| Room temperature is held viscous force/h | 60 | 83 |
| High temperature is held viscous force/min | 200 | 248 |
Embodiment 4
The polycarbonate diol that is 1000 by 100gHDI, 330g molecular weight, at 78 ℃ of reaction 3h, then adds the 5g dimethylolpropionic acid, and reaction 2h obtains base polyurethane prepolymer for use as; By the double bond containing modification E-16 of 10g epoxy resin, Hydroxyethyl acrylate 15 joins in this performed polymer, under 75 ℃ with prepolymer reaction 5h, obtain the base polyurethane prepolymer for use as of modification, then be cooled to 40 ℃, add in the 3g triethylamine and 20min, add the 309g deionized water under the 5500r/min rotating speed, disperse 10min, obtain modified aqueous polyurethane dispersoid.Evenly drip the 40g butyl acrylate in this modified aqueous polyurethane dispersoid, the Gum Rosin of 16g modification and 0.4g Ammonium Persulfate 98.5,75 ℃ of reaction 3.5h, be warming up to again 90 ℃ of insulation reaction 1 hour, be down to room temperature, discharging is also filtered, and obtains the aqueous polyurethane dispersion of modification.The preparation of modified rosin resin: rosin and Resorcinol are added to be had agitator, in the conversion unit of thermometer and condenser, begins slowly to heat up, when temperature of reaction is raised to 220 ℃, drip lentamente again vinylformic acid, after dripping, then insulation, cool the temperature to 150 ℃ of dischargings; Rosin, Resorcinol and acrylic acid mass ratio are 100:2:5.Rosin is selected the superfine rosin of acid number >=166 (mgKOH/g).Synthesizing of modification E-16 epoxy resin: E-16 epoxy resin is incorporated with in the conversion unit of agitator, thermometer and condenser, adds properties-correcting agent phosphoric acid, under 140 ℃, reaction 2.5h, obtain modification E-16 epoxy resin; The properties-correcting agent addition is 6% of E-16 epoxy resin total amount.
Get the aqueous polyurethane dispersion of the above-mentioned modification of 100g, in this dispersion, add 1g solidifying agent N3600,0.5g defoamer BYK-065/066, obtain the water-based polyurethane adhesive of modification.
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and describes in detail.But the scope of protection of present invention is not limited to the scope that embodiment means.
In these embodiment product performance and prior art, solvent-borne type product SA550 Performance Ratio is in Table 4.As shown in table 4, shown in, its initial bonding strength of the fire resistant water-based pressure sensitive adhesive of product prepared by the present embodiment, 180 ° of peeling forces, room temperatures are held viscous force and high temperature, and to hold the performances such as viscous force suitable with solvent-borne type product SA550, part index number surpasses the solvent-borne type product, the high-performance adhesive tape of making can meet the needs of automobile, electronics industry Pressuresensitive Tape, and preparation technology is simple, be easy to promotion and application.
Table 4
| Quality index | SA550 | The product of the present embodiment |
| Solid content, % | 45 | 50 |
| Initial bonding strength ,/mm | 27 | 29 |
| 180 ° of peeling force/N/25mm | 15 | 17.1 |
| Room temperature is held viscous force/h | 60 | 85 |
| High temperature is held viscous force/min | 200 | 260 |
Claims (10)
1. the preparation method of the high-temperature resistant waterborne polyurethane pressure sensitive adhesive of a modification, is characterized in that, comprises the steps:
(1) preparation of base polyurethane prepolymer for use as: add polyisocyanates and oligomer polyol in conversion unit, react 2～3h under 60～80 ℃, then add wetting ability chainextender reaction 2～5h, obtain base polyurethane prepolymer for use as, wherein, the ratio of polyisocyanates and oligomer polyol amount of substance is 2.5～1.2:1; The mass ratio of polyisocyanates and chainextender is 10:0.5～1.5; Described oligomer polyol is polyester polyol or polyether glycol; Or described oligomer polyol is polybutadiene diol; Described wetting ability chainextender is dihydroxymethyl acetic acid, dimethylol propionic acid or dimethylolpropionic acid;
(2) base polyurethane prepolymer for use as of modification is synthetic: under 60～80 ℃, the acrylate of hydroxyl and modified epoxy are added in the base polyurethane prepolymer for use as that step (1) obtains and react 3～5h, then be cooled to 30-40 ℃, add in neutralizing agent and 10～20min, obtain the base polyurethane prepolymer for use as of modification, wherein, the mass ratio of the acrylate of polyisocyanates, hydroxyl, modified epoxy and neutralizing agent is 10:1～1.5:0.5～1:0.2～0.6; Synthesizing of described modified epoxy: epoxy resin is added in conversion unit, then add properties-correcting agent, under 120～150 ℃, react 2～3h, obtain the epoxy resin of modification; The properties-correcting agent addition is 1～10% of epoxy resin quality; Described properties-correcting agent is phosphoric acid or acetic acid;
(3) aqueous polyurethane dispersion is synthetic: in the modified polyurethane prepolymer after the neutralization obtained to step (2), add water, with high speed dispersor speed dispersion and emulsion 10～30min with 3000～5500rpm/min under 35 ℃～40 ℃, obtain aqueous polyurethane dispersion, the quality of described water is 40～45% for making this aqueous polyurethane dispersion solid content;
(4) preparation of the aqueous polyurethane dispersion of modification: in described aqueous polyurethane dispersion, evenly drip acrylate monomer, modified rosin resin and initiator, 70～75 ℃ of reaction 3～4h, then be warming up to 80～90 ℃, reaction 1～1.5h, lower the temperature again, discharging filter, obtain modified aqueous polyurethane dispersoid; The solid ingredient of described acrylate monomer, modified rosin resin, aqueous polyurethane dispersion and the mass ratio of initiator are 10～20:5～10:100:0.1～0.3; Described initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or benzoyl peroxide; The preparation of described modified rosin resin: rosin and Resorcinol are added in conversion unit, while being warmed up to 220 ℃-240 ℃, drip vinylformic acid, insulation, cool the temperature to 145-155 ℃ of discharging; Rosin, Resorcinol and acrylic acid mass ratio are 100:1～3:1～8;
(5) preparation of the aqueous polyurethane high temperature resistant pressure sensitive adhesive of modification: in described modified aqueous polyurethane dispersoid, add defoamer, obtain multiple modified aqueous polyurethane dispersion, external reinforcement agent again, obtain the double-component waterborne polyurethane pressure sensitive adhesive of heat resist modification; The mass ratio of described solidifying agent, modified aqueous polyurethane dispersoid and defoamer is 0.5～1:100:0.1～0.5; Described defoamer is the silicone oil defoamer; Described solidifying agent is isocyanate curing agent.
2. preparation method according to claim 1, it is characterized in that, the polyisocyanates of described step (1) is tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditan-4,4 ˊ-vulcabond, poly methylene poly phenyl poly isocyanate or xylylene diisocyanate.
3. preparation method according to claim 1, it is characterized in that, described polyester polyol comprises polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-BDO esterdiol, glycol ether esterdiol, polycarbonate diol or polycaprolactone glycol.
4. preparation method according to claim 1, is characterized in that, described polyether glycol is polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
5. preparation method according to claim 1, is characterized in that, described epoxy resin is epoxy resin E-16, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51.
6. preparation method according to claim 1, is characterized in that, the acrylate of described hydroxyl is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 or Propylene glycol monoacrylate.
7. preparation method according to claim 1, is characterized in that, the neutralizing agent of described step (2) is triethylamine or trolamine.
8. preparation method according to claim 1, is characterized in that, described acrylate monomer is ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer.
9. preparation method according to claim 1, is characterized in that, described defoamer is ATF-1, ATF-2, BYK-141 and BYK-065/066 defoamer.
10. according to the described preparation method of right 1, it is characterized in that the isocyanate curing agent that described solidifying agent is N3200, N3300, N3400 or N3600.
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| CN108570281A (en) * | 2018-03-27 | 2018-09-25 | 华南理工大学 | A kind of bi-component modified aqueous polyurethane flame-retardant coatings glue and preparation method thereof |
| CN108570281B (en) * | 2018-03-27 | 2019-11-15 | 华南理工大学 | A kind of bi-component modified aqueous polyurethane flame-retardant coatings glue and preparation method thereof |
| CN108424731A (en) * | 2018-04-08 | 2018-08-21 | 俞小峰 | A kind of preparation method of pressure sensitive adhesive |
| CN110079264A (en) * | 2019-04-26 | 2019-08-02 | 江苏东邦科技有限公司 | Automobile inside solid |
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| CN110358491A (en) * | 2019-08-01 | 2019-10-22 | 宁波心维标签制品有限公司 | A kind of pressure sensitive adhesive and preparation method thereof for label paper during fresh cold chain |
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| CN113105850A (en) * | 2021-03-12 | 2021-07-13 | 华南理工大学 | Waterborne polyurethane-acrylate-epoxidized soybean oil label adhesive and preparation method thereof |
| CN113105850B (en) * | 2021-03-12 | 2022-07-12 | 华南理工大学 | Waterborne polyurethane-acrylate-epoxidized soybean oil label adhesive and preparation method thereof |
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