CN103031093B - Method for preparing water-based urethane acrylate pressure-sensitive adhesive - Google Patents
Method for preparing water-based urethane acrylate pressure-sensitive adhesive Download PDFInfo
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Abstract
The invention provides a method for preparing water-based urethane acrylate pressure-sensitive adhesive. According to the method, water-based urethane is chemically modified by using acrylate, and the water-based urethane and the acrylate are combined with each other in a chemical bond form, so that the synthesized water-based urethane acrylate pressure-sensitive adhesive has excellent performance of the water-based urethane and the acrylate. According to the water-based urethane acrylate pressure-sensitive adhesive, water-based urethane acrylate copolymerization emulsion and tackifying resin are used as main components. The method comprises the following steps of: firstly, reacting a hydroxy monomer, a hydrophilic chain extender and polyisocyanate which are used as main raw materials to generate polyurethane prepolymer, and adding a hydroxy-containing acrylate monomer to obtain hydroxy-terminated polyurethane prepolymer; secondly, adding a salt-forming agent to neutralize the hydroxy-terminated polyurethane prepolymer, and dispersing in water to obtain water-based polyurethane emulsion; and finally, properly polymerizing the water-based polyurethane emulsion and the acrylate to obtain the water-based urethane acrylate copolymerization emulsion, and adding the tackifying resin of different mass fractions, thereby obtaining water-based urethane acrylate pressure-sensitive adhesive emulsion.
Description
Technical field
The invention belongs to Aqueous Adhesives preparing technical field, be specifically related to the preparation method of aqueous polyurethane acrylate pressure sensitive adhesive.
Background technology
Aqueous Polyurethane Adhesives is the important class in Aqueous Adhesives, has the premium properties of polyurethane material.Aqueous Polyurethane Adhesives contains the isocyanate group and urethano that polarity is very strong, chemical activity is very high, and make it to have excellent chemical adhesive power, it is free from environmental pollution, and Application Areas, purposes are also more and more wide.But its resistance to elevated temperatures, water resistance and the poor-performing of resistance to outdoor aging.And acrylate (PA) has good water tolerance, weathering resistance and resistance to outdoor aging, poor performance at low temperatures.Utilize the complementarity in aqueous polyurethane and acrylate performance, adopt acrylate to carry out modification to urethane resin, aqueous polyurethane-acrylate (PUA) composite emulsion of availability excellence
CN.102516486A discloses the preparation method of the emulsion pressure-sensitive of liquid crystal protective film acrylate quasi-oligomer and polyurethane copolymerization; method first carboxylic monomer, hydrophilic chain extender and isocyanate-monomer is reacted; then add acrylate quasi-oligomer and carry out graft copolymerization; then add the prepolymer after polyhydric linking agent and graft copolymerization and carry out crosslinking reaction, finally by add in salt forming agent and after be emulsifiable in water chain extension and form the acrylate quasi-oligomer of transparent or semitransparent blueing light and the emulsion pressure-sensitive of aqueous polyurethane copolymerization.The method can improve the transformation efficiency of acrylic ester monomer preferably, but in its process, the control of R value is loaded down with trivial details, and degree of crosslinking controls not easily, and needs additional crosslink agent.
CN.1869139A describes a kind of preparation method of ultraviolet light solidfication water polyurethane-acrylate, mainly by polyoxyethylene glycol, multi-hydroxy carboxy acid and aromatic diisocyanate are obtained by reacting polyurethane prepolymer, and then drip in prepolymer and obtain polyurethane-acrylate oligopolymer containing the hydroxyethyl methylacrylate of stopper or Rocryl 410, be emulsifiable in water finally by salify neutralization and obtain aqueous polyurethane acrylate tackiness agent.The problem of the method is that Acrylic Acid Monomer adds rear being difficult to and is polymerized completely, and in emulsion, Acrylic Acid Monomer residual quantity is large, does not meet and cleans explained hereafter requirement.
Summary of the invention
The invention provides a kind of preparation method of aqueous polyurethane acrylate pressure sensitive adhesive.With acrylate chemistry modified aqueous polyurethane, make to combine with chemical bond form between the two, make the aqueous polyurethane acrylate pressure sensitive adhesive synthesized have the excellent properties of aqueous polyurethane and acrylate.
Aqueous polyurethane acrylate pressure sensitive adhesive, with aqueous polyurethane acrylate copolymer emulsion and tackifying resin for main component, main with carboxylic monomer, hydrophilic chain extender and polyisocyanates are main raw material, reaction adds the acrylate monomer of hydroxyl after generating base polyurethane prepolymer for use as, obtain hydroxyl-terminated polyurethane performed polymer, then, by to add in salt forming agent and after in water dispersion obtain aqueous polyurethane emulsion, suitable being polymerized is carried out finally by with acrylate, obtain aqueous polyurethane acrylate copolymer emulsion, add the tackifying resin of different mass mark again thus obtain aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.
The preparation method of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion, carries out according to following step:
(A) preparation of preparation (B) the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion of aqueous polyurethane emulsion.
(A) preparation of aqueous polyurethane emulsion:
1. carboxylic monomer and hydrophilic chain extender mixing are warming up to 140 ~ 160 DEG C, dehydration, after 10 ~ 20min, is cooled to 50 ~ 70 DEG C, adds the isocyanate-monomer of metering, be warming up to 80 ~ 90 DEG C, constant temperature 2 ~ 2.5h;
Wherein said carboxylic monomer is polyether glycol, polyester polyol or both mixtures.
Wherein said hydrophilic chain extender is the small molecule polyol containing carboxyl, sulfonic acid group or sulfonate groups, its quality account for isocyanate-monomer, carboxylic monomer, hydrophilic chain extender three total mass 5.5% ~ 15.5%;
Wherein said isocyanate-monomer is aromatic polyisocyanate, aliphatic polyisocyante or alicyclic polyisocyanates, and its quality is with control R
1value is 1.2 ~ 1.8 to calculate as benchmark.(R
1value refers to the ratio not adding-NCO and-OH in end-capping reagent system);
2. to the acrylate monomer reaction 2 ~ 3h adding hydroxyl in 1., after reaction terminates, add organic solvent and regulate viscosity, add salt forming agent, stir 10 ~ 30min, base polyurethane prepolymer for use as is added to the water and carries out dispersion chain extension 2 ~ 3h, obtain aqueous polyurethane emulsion;
The acrylate monomer of wherein said hydroxyl is Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410; Its quality is with control R
2value is 1 ~ 1.8 calculate (R as benchmark
2value is the ratio of-NCO and-OH in system when adding end-capping reagent);
Wherein said organic solvent comprises acetone, butanone, tetrahydrofuran (THF), di-alcohol dme, acetonitrile, ethylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, ether, sherwood oil or ethyl acetate; Its quality is 60% ~ 80% of carboxylic monomer quality.
Wherein said salt forming agent comprises triethylamine, dimethylethanolamine, diethanolamine, methylamine, ammoniacal liquor, sodium hydroxide or potassium hydroxide; Wherein control degree of neutralization, namely salt forming agent monomer is 36% ~ 120% of hydrophilic chain extender monomer molar amount;
(B) preparation of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
Weigh the aqueous polyurethane emulsion obtained early stage, temperature rises to 40 ~ 80 DEG C, and drip the esters of acrylic acid being dissolved with metering initiator of metering, drip after terminating, constant temperature 2 ~ 3h, obtains aqueous polyurethane acrylate copolymer emulsion; The tackifying resin adding different mass mark again mixes, and namely obtains aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion;
Wherein said esters of acrylic acid is acrylate or methacrylic ester, and its quality accounts for 0% ~ 90% of aqueous polyurethane emulsion quality;
Wherein said initiator comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide or hydrogen peroxide, and initiator quality is 2% of esters of acrylic acid quality;
Wherein said tackifier resin emulsion is commercially available water dispersible or oil-soluble Gum Rosin, hydrogenated rosin resin, terpine resin, C5 petroleum resin, polymer resin or rosin/C5 copolymer resins, and its quality is 0 ~ 30% of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion aqueous polyurethane emulsion quality.
Step 1. described in polyether glycol be copolymerization dibasic alcohol or the polyvalent alcohol of polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or above-mentioned monomer; Polyester polyol is polyethylene glycol adipate glycol, poly-hexanodioic acid-BDO esterdiol or polyhexamethylene adipate glycol.
The 1. described hydrophilic chain extender of step is dimethylol propionic acid, dimethylolpropionic acid, BDO-2-sodium sulfonate, 1,2-PD-3-sodium sulfonate or thionamic acid sodium;
The 1. described aromatic polyisocyanate of step is tolylene diisocyanate or 4,4 ∕-diphenylmethanediisocyanate; Aliphatics or alicyclic polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate or xylylene diisocyanate.
Acrylate described in step B comprises methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n-propyl or Isooctyl acrylate monomer; Methacrylic ester comprises Tert-butyl Methacrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate or n-BMA.
The present invention has prepared aqueous polyurethane acrylate pressure sensitive adhesive, esters of acrylic acid is incorporated in polyurethane system, achieve both intermolecular compatible, combine the characteristic of aqueous polyurethane and esters of acrylic acid, thus obtain the composite pressure sensitive adhesive emulsion having aqueous polyurethane and the common excellent properties of acrylate concurrently, and after in the end the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion of our selectivity optimum mixes with the tackifying resin of different ratios, first sticky and 180 ° of strippings of aqueous polyurethane acrylate pressure sensitive adhesive are further improved and aqueous polyurethane pressure sensitive adhesive are more widely used.Compared with solvent pressure-sensitive adhesive, aqueous polyurethane acrylate class pressure sensitive adhesive is solvent with water, decreases the use of organic solvent, both reduces industrial cost, also meets the needs of process for cleanly preparing; Compared with hydridization type aqueous polyurethane acrylate class pressure sensitive adhesive, such pressure sensitive adhesive improves the transformation efficiency of acrylic ester monomer, better the performance of acrylate and aqueous polyurethane is combined, such as, the mechanical property, solvent resistance etc. of product are obtained for effective raising.
Embodiment
Below by specific embodiment, the invention will be further described, but be not limited to this.
The each embodiment of following the present invention will divide two portions to further illustrate, i.e. the preparation of aqueous polyurethane emulsion and the preparation of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.
Embodiment 1:(is wherein: R
1value is 1.2, R
2value is massfraction shared by 1, DMPA is 8%, and degree of neutralization is 100%, and massfraction shared by acrylate is 90%)
(A) preparation of aqueous polyurethane emulsion
Get the polypropylene glycol-1000(PPG-1000 of 0.025mol), 0.022mol dimethylol propionic acid (DMPA) is added in the four-hole boiling flask that stirring is housed and is warming up to 140 DEG C, dehydration, after about 10min, be cooled to 60 DEG C, add the TDI of 0.0564mol, be warming up to 80 DEG C, constant temperature 2.5h, stop heating, Temperature fall is to 70 DEG C, add 1.222g Propylene glycol monoacrylate (HPA), reaction about 2h.After end capping terminates, add butanone and regulate viscosity, butanone quality is 60% of polypropylene glycol quality, adds 0.022mol triethylamine, stirs about 10min, is added by base polyurethane prepolymer for use as in 155g water and carries out dispersion chain extension and be about 2h, obtain aqueous polyurethane emulsion.
(B) preparation (tackifying resin add-on is 0%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that weighing 100g obtains in earlier stage, in four-hole boiling flask, is warming up to about 75 DEG C, drips the Isooctyl acrylate monomer (being dissolved with the AIBN of 1.8g) of 90g, and drip after terminating, constant temperature 2h, obtains aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.Test result is as table 1.
Embodiment 2:(is R wherein
1value is 1.4, R
2value is massfraction shared by 1, DMBA is 7%, and degree of neutralization is 80%, and massfraction shared by acrylate is 15%)
(A) preparation of aqueous polyurethane emulsion
Get the polypropylene glycol-2000(PPG-2000 of 0.025mol), 0.022mol dimethylolpropionic acid (DMBA) is added in the four-hole boiling flask that stirring is housed and is warming up to 160 DEG C, dehydration, after about 15min, be cooled to 50 DEG C, add the MDI of 0.065mol, be warming up to 90 DEG C, constant temperature 2h, stop heating, Temperature fall is to 70 DEG C, add 2.34g hydroxyethyl methylacrylate (HEMA), reaction about 2h.After end capping terminates, add acetone and regulate viscosity, acetone quality is 70% of polypropylene glycol quality, add 0.0176mol dimethylethanolamine, stir about 10min, base polyurethane prepolymer for use as is added in 158g water and carry out dispersion chain extension and be about 3h, obtain aqueous polyurethane emulsion.
(B) preparation (tackifying resin add-on is 0%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains, in four-hole boiling flask, is warming up to about 75 DEG C, drips the n-propyl (being dissolved with the 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.3g) of 15g, and drip after terminating, constant temperature 3h, obtains aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.Test result is as table 1.
Embodiment 3:(is R wherein
1value is 1.4, R
2value is 1.1, and shared by BDO-2-sodium sulfonate, massfraction is 10.5%, and degree of neutralization is 86%, and massfraction shared by acrylate is 45%)
(A) preparation of aqueous polyurethane emulsion
Get Polyethylene glycol-2000 (PEG-2000), the 0.022mol1 of 0.025mol, 4-butyleneglycol-2-sodium sulfonate is added in the four-hole boiling flask that stirring is housed and is warming up to 150 DEG C, and dehydration, after about 10min, be cooled to 65 DEG C, add the hexamethylene diisocyanate (HDI) of 0.065mol, be warming up to 85 DEG C, constant temperature 2.5h, stop heating, Temperature fall, to 70 DEG C, adds 1.17g Rocryl 410 (HPMA), reaction about 3h.After end capping terminates, add tetrahydrofuran (THF) and regulate viscosity, tetrahydrofuran (THF) quality is that 80% of polyoxyethylene glycol quality adds 0.0189mol diethanolamine, stirs about 20min, base polyurethane prepolymer for use as is added in 157g water and carry out dispersion chain extension and be about 3h, obtain unsaturated aqueous polyurethane emulsion.
(B) preparation (tackifying resin add-on is 0%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains, in four-hole boiling flask, is warming up to about 75 DEG C, drips the sec-butyl acrylate (being dissolved with the dibenzoyl peroxide of 0.9g) of 45g, drips after terminating, constant temperature 2h, aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.Test result is as table 1.
Embodiment 4:(is R wherein
1value is 1.4, R
2value is 1.4, and shared by 1,2-PD-3-sodium sulfonate, massfraction is 15.5%, and degree of neutralization is 36%, and massfraction shared by acrylate is 22.5%)
(A) preparation of aqueous polyurethane emulsion
Get the polypropylene glycol-3000(PPG-3000 of 0.025mol), 0.055mol1, 2-propylene glycol-3-sodium sulfonate is added in the four-hole boiling flask that stirring is housed and is warming up to 160 DEG C, dehydration, after about 10min, be cooled to 60 DEG C, add the isophorone diisocyanate (IPDI) of 0.128mol, be warming up to 90 DEG C, constant temperature 2.5h, stop heating, Temperature fall is to 70 DEG C, add di-alcohol dme and regulate viscosity, methyl ether quality is 80% of polypropylene glycol quality, add 0.0198mol methylamine, stir about 10min, base polyurethane prepolymer for use as is added in 155g water and carry out dispersion chain extension and be about 3h, obtain aqueous polyurethane emulsion.
(B) preparation (tackifying resin add-on is 0%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains, in four-hole boiling flask, is warming up to about 75 DEG C, drips the methacrylic ester (being dissolved with the AIBN of 0.45g) of 22.5g, and drip after terminating, constant temperature 3h, obtains aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion.Test result is as table 1.
Embodiment 5:(is R wherein
1value is 1.4, R
2value is 1.3, and massfraction shared by thionamic acid sodium is 8.0%, and degree of neutralization is 64%, and massfraction shared by acrylate is 60%)
(A) preparation of aqueous polyurethane emulsion
Get the polytetrahydrofuran diol-2000(PTMG-2000 of 0.025mol), 0.0275mol thionamic acid sodium is added in the four-hole boiling flask that stirring is housed and is warming up to 160 DEG C, dehydration, after about 20min, be cooled to 60 DEG C, add the xylylene diisocyanate (XDI) of 0.065mol, be warming up to 90 DEG C, constant temperature 2h, stop heating, Temperature fall is to 70 DEG C, add 0..406g Propylene glycol monoacrylate (HPA), reaction about 2h.After end capping terminates, add pimelinketone and regulate viscosity, pimelinketone quality is that 60% of polytetrahydrofuran diol quality adds 0.0176mol ammoniacal liquor, stirs about 30min, base polyurethane prepolymer for use as is added in 160g water and carry out dispersion chain extension and be about 3h, obtain aqueous polyurethane emulsion.
(B) preparation (massfraction shared by ester gum resin is 6%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains is in four-hole boiling flask, be warming up to about 75 DEG C, drip the methyl methacrylate (being dissolved with the hydrogen peroxide of 1.2g) of 60g, after dropping terminates, constant temperature 3h, obtain aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion, then after the ester gum resin agitating adding 6g mixes, obtain the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion containing ester gum resin.Test result is as table 1.
Embodiment 6:(is R wherein
1value is 1.4, R
2value is massfraction shared by 1, DMPA is 7.5%, and degree of neutralization is 90%, and massfraction shared by acrylate is 15%)
(A) preparation of aqueous polyurethane emulsion
Get the polypropylene glycol-2000(PPG-2000 of 0.025mol), 0.022mol dimethylol propionic acid (DMPA) is added in the four-hole boiling flask that stirring is housed and is warming up to 140 DEG C, dehydration, after about 10min, be cooled to 70 DEG C, add the TDI of 0.065mol, be warming up to 90 DEG C, constant temperature 2h, stop heating, Temperature fall is to 70 DEG C, add 2.34g Propylene glycol monoacrylate (HPA), reaction about 2h.After end capping terminates, add ethylene dichloride and regulate viscosity, ethylene dichloride quality is 80% of polypropylene glycol quality, add 0.0198mol sodium hydroxide, stir about 10min, base polyurethane prepolymer for use as is added in 160g water and carry out dispersion chain extension and be about 3h, obtain aqueous polyurethane emulsion.
(B) preparation (massfraction shared by hydrogenated rosin resin is 15%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains is in four-hole boiling flask, be warming up to about 75 DEG C, drip the β-dimethyl-aminoethylmethacrylate (being dissolved with the AIBN of 0.3g) of 15g, after dropping terminates, constant temperature 2h, obtaining β-dimethyl-aminoethylmethacrylate ester amount mark is 140% aqueous polyurethane β-dimethyl-aminoethylmethacrylate pressure sensitive adhesion agent emulsion, then after the hydrogenated rosin resin adding 15g mixes, obtains the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion containing hydrogenated rosin resin.Test result is as table 1.
Embodiment 7:(is R wherein
1value is 1.4, R
2value is massfraction shared by 1, DMPA is 5.5%, and degree of neutralization is 80%, and massfraction shared by acrylate is 30%)
(A) preparation of aqueous polyurethane emulsion
Get the polypropylene glycol-2000(PPG-2000 of 0.025mol) and PEG-6000 (PEG-1000) mixture (both blending ratios are mol ratio 5:5), 0.022mol dimethylol propionic acid (DMPA) is added in the four-hole boiling flask that stirring is housed and is warming up to 160 DEG C, remove small molecules and dissolve DMPA, after about 10min, be cooled to 60 DEG C, add the TDI of 0.065mol, be warming up to 80 DEG C, constant temperature 2.5h, stop heating, Temperature fall, to 70 DEG C, adds 2.34g Propylene glycol monoacrylate (HPA), reaction about 2h.After end capping terminates, add butanone and regulate viscosity, butanone quality is 70% of polypropylene glycol quality, adds 0.0176mol triethylamine, stirs about 10min, is added by base polyurethane prepolymer for use as in 160g water and carry out dispersion chain extension about 2 ~ 3h, obtain aqueous polyurethane emulsion.
(B) preparation (shared by C5 petroleum resin quality, mark is 1.5%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains is in four-hole boiling flask, be warming up to about 75 DEG C, drip the Isooctyl acrylate monomer (being dissolved with the AIBN of 0.6g) of 30g, after dropping terminates, constant temperature 3h, obtain aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion, then after the C5 petroleum resin adding 1.5g are uniformly mixed, obtain the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion containing C5 petroleum resin.Test result is as table 1.
Embodiment 8:(is R wherein
1value is 1.4, R
2value is massfraction shared by 1.2, DMPA is 7.5%, and degree of neutralization is 120%, and massfraction shared by acrylate is 0%)
(A) preparation of aqueous polyurethane emulsion
Polyethylene glycol-2000 (PEG-2000), the 0.022mol dimethylol propionic acid (DMPA) of getting 0.025mol are added in the four-hole boiling flask that stirring is housed and are warming up to 140 DEG C, dehydration, after about 10min, be cooled to 60 DEG C, add the TDI of 0.065mol, be warming up to 80 DEG C, constant temperature 2h, stop heating, Temperature fall is to 70 DEG C, add 1.17g Propylene glycol monoacrylate (HPA), reaction about 2h.After end capping terminates, add butanone and regulate viscosity, butanone quality is 60% of polyoxyethylene glycol quality, adds 0.0264mol triethylamine, stirs about 10min, is added by base polyurethane prepolymer for use as in 160g water and carries out dispersion chain extension and be about 2h, obtain aqueous polyurethane emulsion.
(B) preparation (massfraction shared by terpine resin is 3%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
Weigh the emulsion that in earlier stage of 100g obtains in four-hole boiling flask, after the terpine resin adding 3g is uniformly mixed, obtain the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion containing terpine resin.Test result is as table 1.
Embodiment 9:(is R wherein
1value is 1.8, R
2value is massfraction shared by 1.8, DMPA is 7%, and degree of neutralization is 100%, and massfraction shared by acrylate is 22.5%)
(A) preparation of aqueous polyurethane emulsion
Get the polyoxyethylene glycol-3000(PEG-3000 of 0.025mol), 0.022mol dimethylol propionic acid (DMPA) is added in the four-hole boiling flask that stirring is housed and is warming up to 160 DEG C, dehydration, after about 10min, be cooled to 60 DEG C, add the TDI of 0.085mol, be warming up to 80 DEG C, constant temperature 2h, stop heating, Temperature fall is to 70 DEG C, and add butanone and regulate viscosity, butanone quality is 80% of polyoxyethylene glycol quality, add 0.022mol triethylamine, stir about 10min, base polyurethane prepolymer for use as is added in 163g water and carry out dispersion chain extension and be about 3h, obtain aqueous polyurethane emulsion.
(B) preparation (massfraction shared by water-based terpine resin is 30%) of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
The emulsion that the early stage weighing 100g obtains is in four-hole boiling flask, be warming up to about 75 DEG C, drip the Isooctyl acrylate monomer (being dissolved with the AIBN of 0.45g) of 22.5g, after dropping terminates, constant temperature 3h, obtain watersoluble polyurethane acrylic acid different monooctyl ester pressure sensitive adhesion agent emulsion, then after the water-based terpine resin adding 30g is uniformly mixed, obtain the aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion containing water-based terpine resin.Test result is as table 1.
Testing method: the preparation of pressure sensitive adhesive: get appropriate emulsion glass stick uniform application in polyester film surface, dry 2h in 65 DEG C of baking ovens, takes out and is attached to test after test board upper 24 hour.Just sticky mensuration: measure with reference to GB/T4852-2002.Adopt inclined-plane rolling ball method to test, be horizontally fixed on by grounder device on test board, standard angle 30 ° is got on scarp.The mensuration of stripping strength: test according to GB/T2792-1998.Batten is wide is 25mm, and sample free end and test board are clipped on BLD-2005 electron detachment machine respectively and test, loading velocity 50mm/min, probe temperature is 20 DEG C.The mensuration of solvent resistance: the film of known quality is placed in respectively water, 5% sodium hydroxide solution, 5% hydrochloric acid, acetone, ethyl acetate, toluene soaks 24h, observe its change, and weigh, calculate rate of body weight gain.
Table 1
The rate of moisture absorption of polyurethane-acrylate film prepared by table 2 embodiment 6
Claims (5)
1. a preparation method for aqueous polyurethane acrylate pressure sensitive adhesive, is characterized in that: step is as follows:
(A) preparation of aqueous polyurethane emulsion: 1. carboxylic monomer and hydrophilic chain extender mixing are warming up to 140 ~ 160 DEG C, dehydration, after 10 ~ 20min, is cooled to 50 ~ 70 DEG C, adds the isocyanate-monomer of metering, be warming up to 80 ~ 90 DEG C, constant temperature 2 ~ 2.5h;
Wherein said carboxylic monomer is polyether glycol, polyester polyol or both mixtures;
Wherein said hydrophilic chain extender is the small molecule polyol containing carboxyl, sulfonic acid group or sulfonate groups, its quality account for isocyanate-monomer, carboxylic monomer, hydrophilic chain extender three total mass 5.5% ~ 15.5%;
Wherein said isocyanate-monomer is aromatic polyisocyanate, aliphatic polyisocyante or alicyclic polyisocyanates, wherein control R
1value is 1.2 ~ 1.8;
2. to the acrylate monomer reaction 2 ~ 3h adding hydroxyl in 1., after reaction terminates, add organic solvent and regulate viscosity, add salt forming agent, stir 10 ~ 30min, base polyurethane prepolymer for use as is added to the water and carries out dispersion chain extension 2 ~ 3h, obtain aqueous polyurethane emulsion;
The acrylate monomer of wherein said hydroxyl is Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410; Wherein control R
2value is 1-1.8;
Wherein said organic solvent comprises acetone, butanone, tetrahydrofuran (THF), di-alcohol dme, acetonitrile, ethylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, ether, sherwood oil or ethyl acetate, and its quality is 60% ~ 80% of carboxylic monomer quality;
Wherein said salt forming agent comprises triethylamine, dimethylethanolamine, diethanolamine, methylamine, ammoniacal liquor, sodium hydroxide or potassium hydroxide; Wherein controlling degree of neutralization is 36% ~ 120%;
(B) preparation of aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion
Weigh the aqueous polyurethane emulsion obtained early stage, temperature rises to 40 ~ 80 DEG C, and drip the esters of acrylic acid being dissolved with metering initiator of metering, drip after terminating, constant temperature 2 ~ 3h, obtains aqueous polyurethane acrylate copolymer emulsion; The tackifying resin adding different mass mark again mixes, and namely obtains aqueous polyurethane acrylate pressure sensitive adhesion agent emulsion;
Wherein said esters of acrylic acid is acrylate or methacrylic ester, and quality accounts for 0% ~ 90% of aqueous polyurethane emulsion quality;
Wherein said initiator comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide or hydrogen peroxide, and initiator quality is 2% of esters of acrylic acid quality;
Wherein said tackifier resin emulsion is commercially available water dispersible or oil-soluble Gum Rosin, hydrogenated rosin resin, terpine resin, C5 petroleum resin, polymer resin or rosin/C5 copolymer resins, and quality is 0 ~ 30% of aqueous polyurethane emulsion quality.
2. the preparation method of aqueous polyurethane acrylate pressure sensitive adhesive according to claim 1, is characterized in that: step 1. described in polyether glycol be copolymerization dibasic alcohol or the polyvalent alcohol of polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or above-mentioned monomer; Polyester polyol is polyethylene glycol adipate glycol, poly-hexanodioic acid-BDO esterdiol or polyhexamethylene adipate glycol.
3. the preparation method of aqueous polyurethane acrylate pressure sensitive adhesive according to claim 1, it is characterized in that: the 1. described hydrophilic chain extender of step is dimethylol propionic acid, dimethylolpropionic acid, 1,4-butyleneglycol-2-sodium sulfonate, 1,2-PD-3-sodium sulfonate or thionamic acid sodium.
4. the preparation method of aqueous polyurethane acrylate pressure sensitive adhesive according to claim 1, is characterized in that: the 1. described aromatic polyisocyanate of step is tolylene diisocyanate or 4,4/-diphenylmethanediisocyanate; Aliphatics or alicyclic polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate or xylylene diisocyanate.
5. the preparation method of aqueous polyurethane acrylate pressure sensitive adhesive according to claim 1, is characterized in that: the acrylate described in step B comprises methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n-propyl or Isooctyl acrylate monomer; Methacrylic ester comprises Tert-butyl Methacrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate or n-BMA.
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| CN201210534917.0A CN103031093B (en) | 2012-12-12 | 2012-12-12 | Method for preparing water-based urethane acrylate pressure-sensitive adhesive |
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| CN201210534917.0A CN103031093B (en) | 2012-12-12 | 2012-12-12 | Method for preparing water-based urethane acrylate pressure-sensitive adhesive |
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| CN103031093B true CN103031093B (en) | 2014-12-24 |
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| CN201210534917.0A Active CN103031093B (en) | 2012-12-12 | 2012-12-12 | Method for preparing water-based urethane acrylate pressure-sensitive adhesive |
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