CN1292038C - Hydrophilic polyurethane pressure-sensitive adhesive and preparing method thereof - Google Patents
Hydrophilic polyurethane pressure-sensitive adhesive and preparing method thereof Download PDFInfo
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- CN1292038C CN1292038C CNB031191029A CN03119102A CN1292038C CN 1292038 C CN1292038 C CN 1292038C CN B031191029 A CNB031191029 A CN B031191029A CN 03119102 A CN03119102 A CN 03119102A CN 1292038 C CN1292038 C CN 1292038C
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Abstract
The present invention provides hydrophilic polyurethane pressure-sensitive adhesive and a preparation method thereof. In polyurethane polyol prepared from polyurethane which is formed from at least three kinds of polymer polyol by the irregular bonding of diisocyanate, low molecular diamine or a polymer thereof, one kind of polymer polyol is polyglycol or a derivative thereof; one kind of polymer polyol is hydrophobic macromolecular dibasic alcohol; one kind of polymer polyol is macromolecular polyol containing at least three hydroxy groups. Butanone is adopted as a solvent. First, the diisocyanate and the macromolecular polyol are condensed and polymerized to form a prepolymer with a-NCO group; then, polyurethane is prepared from the low molecular diamine or the polymer thereof by chain propagation. The hydrophilic polyurethane pressure-sensitive adhesive is characterized in that the hydrophilic polyurethane pressure-sensitive adhesive has the performance of hydrophilicity, repeated pasting performance, favorable skin compatibility, etc. The defects of hydrophobic pressure-sensitive adhesive are overcome. The pressure-sensitive adhesive can be independently used, or can be physically combined with one or multiple components of a water-soluble polymer, a surfactant, hydrogel, a nanometer particle or a micelle to be used as medical and medicinal pressure-sensitive adhesive.
Description
Technical field
The present invention relates to polyurethane copolymer pressure sensitive adhesive of a kind of random block and preparation method thereof.This pressure sensitive adhesive has good absorbent ventilate, attaches comfortablely, is suitable for using as medical, medicinal pressure sensitive adhesive.
Background technology
Up to the 1950's, skin also mainly is the pressure sensitive adhesive of rubber-like with pressure sensitive adhesive.This pressure sensitive adhesive is main raw material with natural or synthetic rubber and adds low-molecular-weight thickening material, softening agent and stablizer etc.Pressure sensitive adhesive with these feedstock production is hydrophobic, can not effectively absorb moisture, therefore can cause pasting position ponding, causes the skin whiting.In addition, the low-molecular-weight component of being added can be infiltrated skin and caused untoward reactions such as allergy.
The appearance of polyacrylate(s) pressure sensitive adhesive is that one of traditional pressure sensitive adhesive is improved greatly, and it has overcome some shortcomings of rubber-like pressure sensitive adhesive.Because this class tackiness agent has autohension, low-molecular-weight materials such as the modifier that therefore needn't interpolation in preparation process can cause allergic reaction, tackifier.But contain unreacted Acrylic Acid Monomer usually in this class pressure sensitive adhesive, this also can cause the stimulation anaphylaxis of skin.Though this class pressure sensitive adhesive is compared with traditional rubber-like pressure sensitive adhesive, absorbent ventilate has had improvement, but still can not absorb moisture and moisture significantly, therefore ought be attached to skin or affected part for a long time, skin still can be come to harm by maceration, and, still exist repeatedly adhibit quality poor, meet water and lose problems such as viscosity.
After this, there is patent (U.S.Pat.No.4,914,173) to report a kind of polyacrylate pressure-sensitive of modification, this pressure sensitive adhesive is by a kind of isocyanate prepolymer and acrylate that has hydroxyl or methacrylic ester reaction, obtains by radiation crosslinking then.Wherein isocyanate prepolymer is by the isocyanic ester and the polyester polyol prepared in reaction of polyfunctionality.This pressure sensitive adhesive can absorb the moisture of 95% (w), can use under the environment of humidity.But the pressure sensitive adhesive tack that obtains by this method is bad, and this has limited its use range.
There is 60 to the seventies pressure sensitive adhesive of a series of commixed type to occur again, can be used to bind up a wound.The pressure sensitive adhesive of patent (U.S.Pat.No.3,339,546) report is water-soluble or meet water swollen colloid and a kind of full-bodied polymkeric substance (as polyisobutene) mixes by one or more.Another kind of pressure sensitive adhesive (U.S.Pat.No.4,551,490) is also by the blend preparation, and component of mixture comprises mixture, styrene block copolymer, mineral oil, water-soluble colloid and the tackifier of polyisobutene or itself and isoprene-isobutylene rubber.This two classes pressure sensitive adhesive can provide the ideal bounding force bonding with skin, and moisture or other body fluid that can absorb epidermis loss comprise wound exudate.The injured skin not though this class pressure sensitive adhesive can attach a couple of days, they also have the shortcoming of self, easily decompose as opaque, fast viscosity difference and when absorbing excess water etc.
Urethane is the reaction product of dibasic alcohol or polyvalent alcohol and vulcabond or polyisocyanates.Although it is widely used on chemical industry, it uses actually rare as pressure sensitive adhesive.This is that traditional polyurethane material does not reach this requirement because the pressure sensitive adhesive requirement has suitable viscosity and elasticity.The polyurethane material of good springiness can not stick to skin surface well, be easy to be stripped from, and the good material of viscosity normally adds excessive polyvalent alcohol in preparation process, and glue is remained on the skin, and lower force of cohesion has limited its use range.
Allen (U.S.Pat.No.4,497,914) has proposed a kind of method for preparing polyurethane contact adhesive.Be to obtain, wherein also add hydrophilic additive such as Mierocrystalline cellulose or natural gum by the oxy-compound of polyisocyanates and two functionality or polyfunctionality (as polyvalent alcohol) reaction by propylene oxide or oxyethane preparation.Because but the hydrophilic additive self that is dispersed in wherein is encapsulated, but therefore absorbed body fluid does not influence the viscosity of urethane.
People's such as Muller patent (U.S.Pat.No.3,930,102) has been reported a kind of polyurethane contact adhesive, can be used to produce label and adhesive tape.This pressure sensitive adhesive has autohension, is to be obtained with aliphatic di-isocyanate reaction by three-functionality-degree alcohol, and wherein NCO/OH is controlled at 0.71～0.85.But this pressure sensitive adhesive does not have enough wetting abilities, can not absorbed body fluid, be not suitable as medical pressure sensitive adhesive.
A kind of polyurethane-base pressure sensitive adhesive that in the recent period patent report arranged with high water-retaining capacity and steam transmitance.Contain excessive hydroxyl in this class pressure sensitive adhesive, second-order transition temperature is about 0 ℃, and water-intake rate reaches 70% (w), is 37 ℃ in temperature, and its steam transmitance is 300g/m under the environment of relative humidity 90%
2/ 24h.The somebody adds a kind of water miscible polymkeric substance that does not contain with isocyanate reaction and prepares pressure sensitive adhesive in above-mentioned polyether polyols with reduced unsaturation in addition, compares on performance with above-mentioned pressure sensitive adhesive to improve.It is comparatively suitable that this class pressure sensitive adhesive has good water-absorbent and stripping strength, can form thin and transparent film through processing.
A kind of polyurethanes pressure sensitive adhesive of patent EP1257590 report is mixture and the isocyanic ester by two kinds of dibasic alcohol, prepares through letex polymerization under the condition that emulsifying agent, catalyzer and chainextender exist.Owing in the reaction raw materials a certain amount of polyoxyethylene glycol is arranged, therefore have certain wetting ability, the absorbent ventilate performance is relatively good.But the crosslinking degree of this pressure sensitive adhesive is too low, can not guarantee the skin required intensity of pressure sensitive adhesive.And emulsifying agent wherein is difficult for removing, and use properties is had certain influence.
Purpose of the present invention just provides a kind of pressure sensitive adhesive that skin is used that is suitable for, and has good water-absorbent and high moisture transmission, consistency preferably, fast viscosity, the intensity that is suitable for using is arranged and take off subsides property etc. repeatedly with skin.
Summary of the invention
The object of the present invention is to provide a kind of skin polyurethane contact adhesive and preparation method thereof.This pressure sensitive adhesive has water-absorbent preferably, higher moisture transmission, and skin irritation not, does not cause allergic reaction.The synthetic method craft of this pressure sensitive adhesive is simple, and easy handling, the product of preparing have good performance and be easy to coating.
The present invention is realized by following technical proposals, it is the hydrophilic polyurethane contact adhesive of a described class, be the urethane that forms by at least three kinds of macromolecular polyols of the random keyed jointing of vulcabond and low molecule diamines or its polymer, it is characterized in that forming in the polyvalent alcohol of urethane, a kind of is polyoxyethylene glycol or the polymkeric substance that contains the polyoxyethylene glycol block, and the relative molecular mass of its polyoxyethylene glycol section is 400～5000; A kind of is the hydrophobicity macromolecule dihydric alcohol, and relative molecular mass is 500～5000; A kind of is the macromolecular polyol that contains at least three hydroxyls, and relative molecular mass is 500～5000.
Above-mentioned hydrophilic polyurethane pressure sensitive adhesive, the relative molecular mass that it is characterized in that polyoxyethylene glycol or contain the polyoxyethylene glycol section in the polymkeric substance of polyoxyethylene glycol block is 800～3000, accounts for 10%～50% of polyvalent alcohol total mass; Hydrophobic macromolecule dihydric alcohol is selected from polytetrahydrofuran diol, polybutadiene diol, polycaprolactone glycol, and its molecular weight is 800～5000, accounts for 20～70% of macromolecular polyol total mass; The macromolecular polyol that contains at least three hydroxyls is polyoxytrimethylene triol or tetrol, and molecular weight is 500～4000, accounts for 1%～25% of polyvalent alcohol total mass, and above-mentioned three kinds of polyvalent alcohol mass percent summations are 100%.
It is chainextender that above-mentioned hydrophilic polyurethane pressure sensitive adhesive adopts low molecule diamines or its polymer, preferred quadrol, butanediamine, hexanediamine, Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine.
This class hydrophilic polyurethane pressure sensitive adhesive, it can be used as skin and uses with pressure sensitive adhesive, can be mixed with the medicine percutaneous absorption patch with drug component, or with water-soluble polymers, tensio-active agent, hydrogel, nanoparticle or micella in one or more component physical combination, regulate pressure sensitive adhesive wetting ability, viscosity, with the consistency of medicine and medicine through the skin release performance, be used to prepare the transdermal formulation of different pharmaceutical.
The preparation method of described hydrophilic polyurethane pressure sensitive adhesive, it is characterized in that the macromolecular polyol mixture is added reactor, dewatered 1～2 hour 100～120 ℃ of following fusion decompressions, below 70 ℃, under the normal pressure, by the hydroxyl mol ratio of isocyanate group and macromolecular polyol is that 1.5～2.0 amount adds vulcabond, and adding butanone, reacted 4～6 hours down at 80 ℃～95 ℃, must hold-base polyurethane prepolymer for use as of NCO group, the mixing solutions that then in system, adds chainextender and butanone, chainextender is low molecule diamines or low molecule diamines polymer, make the isocyanate group of performed polymer and chainextender-NH
2The mol ratio of group is 1～1.1, continues reaction 2～3 hours, and decompression removes butanone then, and discharging obtains thick product, and product is moved in the vacuum drying oven, 90 ℃～100 ℃ following vacuum-dryings 24 hours, obtains transparent solid-state polyurethane contact adhesive.
Used vulcabond is selected from tolylene diisocyanate, 1 among the preparation method of above-mentioned hydrophilic polyurethane pressure sensitive adhesive, hexamethylene-diisocyanate, ditan-4, the derivative of 4 '-vulcabond, isoflurane chalcone diisocyanate and above-mentioned vulcabond, preferred isophorone diisocyanate, hexamethylene diisocyanate.
In this polyurethane contact adhesive preparation, adopt amine chain extender, can improve the intensity of pressure sensitive adhesive and the speed that chain extending reaction carries out like this, and can make the isocyanate group in the system obtain reacting more fully, avoid the residual of free monomer.The amine chain extender that is suitable for preparing this polyurethane contact adhesive is the polymer of small molecules diamines such as quadrol, butanediamine, hexanediamine etc. and these diamines, as Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine etc.
In the preparation process of this pressure sensitive adhesive, adopt ethyl acetate, butanone as the viscosity of solvent, avoid gelatin phenomenon acutely taking place because of reacting with the reduction polymerization system.
Prepared polyurethane contact adhesive possess hydrophilic property can absorb water but water insoluble, dissolves in organic solvents such as ethanol, tetrahydrofuran (THF), butanone.This hydrophilic polyurethane can use with water miscible polymkeric substance, tensio-active agent, hydrogel and nanoparticle or micella blend, the pressure sensitive adhesive that acquisition has suitable viscosity and drug release character, the needs of adaptation different pharmaceutical transdermal absorption formulation.
The pressure sensitive adhesive that makes by above-mentioned preparation method can be coated with 90 ℃～100 ℃ following fusions, the solution that also can be made into its organic solvent such as butanone, ethanol etc. is coated with, therefore the transdermal absorption formulation that is applicable to Chinese medicine, hydrophobicity and water soluble drug is used, and also is applicable to the thermo-sensitivity medicine.Employed back lining materials can be cotton, elastic force cloth, non-woven fabrics and materials such as polyvinyl chloride or polyester film.Coating is transparent, and the surfacing cleaning attaches comfortable.Carrying out the back lining materials that the pressure sensitive adhesive sample of permeability, stripping strength and spin test adopted in the following example is cotton, and the employed back lining materials of sample that is used for the water absorbing properties test is a polyester film.
Embodiment
With embodiment the present invention further is illustrated below.
Example 1:
The adding relative molecular mass is 2000 polytetrahydrofuran diol 64g in a four-hole boiling flask, and relative molecular mass is 1000 polyoxytrimethylene triol 4g, and relative molecular mass is 800 polyoxyethylene glycol 16g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add isophorone diisocyanate 25.7g, butanone 20g reacted 4 hours down at 85 ℃.Add the butanone solution 40g that contains the 3.48g quadrol then.Reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains polyurethane contact adhesive PSA1.
Example 2:
The adding relative molecular mass is 1000 polyoxypropyleneglycol 32g in a four-hole bottle, and relative molecular mass is 3000 polyoxytrimethylene tetrol 5g, and relative molecular mass is 1000 polyoxyethylene glycol 20g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add isophorone diisocyanate 20.78g, butanone 20g reacted 4 hours down at 85 ℃.Add the butanone solution 25g that contains the 2.31g quadrol then, reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.The crude product that will contain a certain amount of solvent moves in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains polyurethane contact adhesive PSA2.
Example 3:
The adding relative molecular mass is 2000 polybutadiene diol 64g in a four-hole bottle, and relative molecular mass is 2000 polyoxytrimethylene triol 4g, and relative molecular mass is 800 polyoxyethylene glycol 16g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add isophorone diisocyanate 18.34g, butanone 20g reacted 4 hours down at 85 ℃.Add Diethylenetriaminee (DETA)/butanone mixing solutions (Diethylenetriaminee (DETA) 2.11g, butanone 25g) then, continue reaction 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains polyurethane contact adhesive PSA3.
Example 4:
The adding relative molecular mass is 2000 polyoxypropyleneglycol 40g in a four-hole bottle, and relative molecular mass is 1000 polyoxytrimethylene triol 3g, and relative molecular mass is 1000 polyoxyethylene glycol 30g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 2 hours.At 65 ℃, under the normal pressure, add hexamethylene diisocyanate 13.8g, butanone 20g reacted 4 hours down at 85 ℃.Add quadrol/butanone mixing solutions (quadrol 2.62g, butanone 30g), reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains polyurethane contact adhesive PSA4.
Example 5:
The adding relative molecular mass is tetrahydrofuran (THF)-propylene oxide copolymerization glycol 80g of 2000 in a four-hole bottle, relative molecular mass is 2000 polyoxytrimethylene triol 8g, relative molecular mass is 800 polyoxyethylene glycol 24g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 2 hours.At 65 ℃, under the normal pressure, add isophorone diisocyanate 33.8g, butanone 20g reacted 5 hours down at 85 ℃.Add quadrol/butanone mixing solutions (quadrol 4.56g, butanone 50g) then, reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains product polyurethane contact adhesive PSA5.
Example 6:
The adding relative molecular mass is 2000 polycaprolactone glycol 32g in a four-hole bottle, and relative molecular mass is 2000 polyoxytrimethylene tetrol 16g, and relative molecular mass is 800 polyoxyethylene glycol 16g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add isophorone diisocyanate 17.3g, butanone 10g reacted 4 hours down at 85 ℃.Add quadrol/butanone mixing solutions (quadrol 1.56g, butanone 20g), reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains polyurethane contact adhesive PSA6.
Example 7:
The adding relative molecular mass is 2000 polytetrahydrofuran diol 60g in a four-hole bottle, and relative molecular mass is 3000 polyoxytrimethylene tetrol 9g, and relative molecular mass is 2000 polyoxyethylene glycol 40g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add hexamethylene diisocyanate 18.8g, butanone 10g reacted 5 hours down at 85 ℃.Add tetraethylenepentamine/butanone mixing solutions (tetraethylenepentamine 7.06g, butanone 70g), reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains product polyurethane contact adhesive PSA7.
Example 8:
The adding relative molecular mass is 2000 polyoxypropyleneglycol 32g in a four-hole bottle, and relative molecular mass is 2000 polyoxytrimethylene tetrol 16g, and relative molecular mass is 1000 polyoxyethylene glycol 20g, and the sealing back is at 120 ℃, and logical nitrogen dewatered 1.5 hours.At 65 ℃, under the normal pressure, add hexamethylene diisocyanate 17.5g, butanone 10g reacted 5 hours down at 85 ℃.Be cooled to 35 ℃, add the butanone solution 40g that contains the 3.12g quadrol, reacted 2 hours.In 70 ℃ of following removal of solvent under reduced pressure butanone, discharging.Crude product is moved in the vacuum drying oven, and at 100 ℃, vacuum tightness 0.1MPa dry 24 hours down obtains product polyurethane contact adhesive PSA8.
Embodiment 9
Take by weighing the polyurethane contact adhesive 10g described in the example 3, relative molecular weight is 400 polyoxyethylene glycol 1g, mixes under 100 ℃, obtains product P SA9 after mixing.
Embodiment 10
Take by weighing the polyurethane contact adhesive 10g described in the example 7, Polyvinylpyrolidone (PVP) (K90,20% aqueous solution) 2.5g mixes under 100 ℃, obtains product P SA10 after mixing.
Embodiment 11
Take by weighing the polyurethane contact adhesive 10g described in the example 6, poloxamer (ploxamer108) 1g mixes under 100 ℃, obtains product P SA11 after mixing.
Embodiment 12
At the polyurethane contact adhesive 10g described in 70 ℃ of following dissolution examples 1, add 5% salicylic acid solution (75% aqueous ethanolic solution) 10g with the dehydrated alcohol of 20mL then, mix concentratedly under 70 ℃, the oven dry of coating back obtains Whitfield's ointment patch TDDs1.
Embodiment 13
Take by weighing the polyurethane contact adhesive 10g described in the example 1, Chinese medicine is coughed and is breathed heavily cream medicinal extract 2.5g, mixes under 90 ℃, is coated with, dries after mixing, and obtains coughing breathing heavily patch agent TDDs2.The The performance test results of pressure sensitive adhesive and transdermal patch is listed in the table 1 in the above-mentioned example.
Table 123 ℃ following pressure sensitive adhesive characteristic
| Water regain (%) | Moisture transmission (g/m 2/24h) | Stripping strength (N) | Spin (#) | |
| PSA1 | 76.5 | 370 | 10.07 | 14 |
| PSA2 | 83.2 | 473 | 7.68 | 16 |
| PSA3 | 84.1 | 360 | 8.76 | 12 |
| PSA4 | 98.7 | 467 | 7.12 | 12 |
| PSA5 | 87.6 | 400 | 8.24 | 13 |
| PSA6 | 80.5 | 340 | 9.27 | 12 |
| PSA7 | 78.3 | 320 | 6.53 | 14 |
| PSA8 | 79.1 | 344 | 6.98 | 12 |
| PSA9 | 97.2 | 455 | 8.31 | 15 |
| PSA10 | 80.1 | 368 | 8.12 | 13 |
| PSA11 | 87.9 | 396 | 7.11 | 15 |
| TDDs1 | 74.1 | 351 | 8.99 | 12 |
| TDDs2 | 80.7 | 402 | 9.01 | 15 |
Annotate:
1. peeling strength test and roller test all adopt national standard
2. following scheme is adopted in the water absorbing properties test:
(1) the even coated testing sample (4 * 4cm of accurate weighing
2) (W
1).
(2) with testing sample glue towards on place the watch-glass of a cleaning, adding distil water was placed 24 hours down for 23 ℃ to the submergence sample
(3) pick and place the sample of putting after 24 hours, shrug off the moisture that surface-moisture is also carefully wiped the polyester film back side away, (W weighs
2)
(4) remove pressure sensitive adhesive through test sample surface, the polyester film of remainder is cleaned up the oven dry (W that weighs
3)
(5) calculate water regain
(6) get three same specification samples and carry out the average water regain of above-mentioned experimental calculation
3. gas permeability test adopts following scheme:
(1) get the known watch-glass of a floorage (s), inject the distilled water of its volume 2/3 therein, (W weighs
1).
(2) get the enough big even coated pressure sensitive adhesive sample of a surface-area, its glue is lived in to state the watch-glass that is filled with water towards water-lute, place 23 ℃, in relative humidity 65% environment, placed 24 hours.
(3) watch-glass (W that seals with pressure sensitive adhesive in the weighing (2)
2).
(4) calculate moisture transmission
Claims (7)
1. hydrophilic polyurethane contact adhesive, be the urethane that forms by at least three kinds of polyvalent alcohols of the random keyed jointing of vulcabond and low molecule diamines or its polymer, it is characterized in that forming in the polyvalent alcohol of urethane, a kind of is polyoxyethylene glycol, and its relative molecular mass is 400～5000; A kind of is the hydrophobicity macromolecule dihydric alcohol, and relative molecular mass is 500～5000; A kind of is the macromolecular polyol that contains at least three hydroxyls, and relative molecular mass is 500～5000.
2. by the described hydrophilic polyurethane pressure sensitive adhesive of claim 1, it is characterized in that the relative molecular mass of polyoxyethylene glycol is 800～3000, account for 10%～50% of polyvalent alcohol total mass; Hydrophobic macromolecule dihydric alcohol is selected from polytetrahydrofuran diol, polybutadiene diol, polycaprolactone glycol, and its molecular weight is 800～5000, accounts for 20～70% of macromolecular polyol total mass; The macromolecular polyol that contains at least three hydroxyls is polyoxytrimethylene triol or tetrol, and molecular weight is 500～4000, accounts for 1%～25% of polyvalent alcohol total mass, and above-mentioned three kinds of polyvalent alcohol mass percent summations are 100%.
3. press the purposes of the described hydrophilic polyurethane pressure sensitive adhesive of claim 1, it is characterized in that it uses with pressure sensitive adhesive as skin, be mixed with the medicine percutaneous absorption patch with drug component, or with water-soluble polymers, tensio-active agent, hydrogel, nanoparticle or micella in one or more component physical combination, regulate pressure sensitive adhesive wetting ability, viscosity, with the consistency of medicine and medicine through the skin release performance, be used to prepare the transdermal formulation of different pharmaceutical.
4. preparation method by the described hydrophilic polyurethane pressure sensitive adhesive of claim 1, its feature comprises following process: polyol blends is added reactor, dewatered 1～2 hour 100～120 ℃ of following fusion decompressions, below 70 ℃, under the normal pressure, by the hydroxyl mol ratio of isocyanate group and macromolecular polyol is that 1.5～2.0 amount adds vulcabond, and adding butanone, reacted 4～6 hours down at 80 ℃～95 ℃, must hold-base polyurethane prepolymer for use as of NCO group, the mixing solutions that then in system, adds chainextender and butanone, chainextender is low molecule diamines or low molecule diamines polymer, make the isocyanate group of performed polymer and chainextender-NH
2The mol ratio of group is 1～1.1, continues reaction 2～3 hours, and decompression removes butanone then, and discharging obtains thick product, and product is moved in the vacuum drying oven, 90 ℃～100 ℃ following vacuum-dryings 24 hours, obtains transparent solid-state polyurethane contact adhesive.
5. press the preparation method of the described hydrophilic polyurethane pressure sensitive adhesive of claim 4, it is characterized in that used vulcabond is selected from tolylene diisocyanate, 1, hexamethylene-diisocyanate, ditan-4, the derivative of 4 '-vulcabond, isophorone diisocyanate and above-mentioned vulcabond.
6. by the preparation method of the described hydrophilic polyurethane pressure sensitive adhesive of claim 5, it is characterized in that used vulcabond is isophorone diisocyanate or hexamethylene diisocyanate.
7. by the preparation method of the described hydrophilic polyurethane pressure sensitive adhesive of claim 4, it is characterized in that the chainextender that adopts is quadrol, butanediamine, hexanediamine, Diethylenetriaminee (DETA), triethylenetetramine or tetraethylenepentamine.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0613333D0 (en) * | 2006-07-05 | 2006-08-16 | Controlled Therapeutics Sct | Hydrophilic polyurethane compositions |
| CN102058895A (en) * | 2009-11-17 | 2011-05-18 | 上海普天欣生物技术有限公司 | Disinfecting active film as well as preparation method and application thereof |
| CN104448219B (en) * | 2013-09-16 | 2018-01-30 | 襄阳三沃航天薄膜材料有限公司 | A kind of waterborne polyurethane resin for pressure sensitive adhesive and preparation method thereof |
| CN106177372A (en) * | 2014-11-10 | 2016-12-07 | 丁永新 | Infection, the hydrophilic pressure sensitive adhesive containing Bulbus Allii volatile oil of promotion wound healing |
| CN104398676A (en) * | 2014-11-10 | 2015-03-11 | 苏州维泰生物技术有限公司 | Hydrophilic pressure-sensitive adhesive containing radix ampelopsis volatile oil and preparation method thereof |
| CN104435041A (en) * | 2014-11-10 | 2015-03-25 | 苏州维泰生物技术有限公司 | Hydrophilic pressure-sensitive adhesive containing alpine yarrow herb volatile oil and preparation method of hydrophilic pressure-sensitive adhesive |
| CN110520498B (en) * | 2017-02-28 | 2022-03-18 | 3M创新有限公司 | Polyurethane adhesive with chemical resistance |
| CN108666502B (en) * | 2018-04-26 | 2021-04-02 | 广东永邦新能源股份有限公司 | Preparation method of hydrophilic heat-resistant lithium battery diaphragm |
| CN108977115A (en) * | 2018-08-01 | 2018-12-11 | 深圳日高胶带新材料有限公司 | A kind of waterborne polyurethane pressure-sensitive adhesives and the preparation method and application thereof |
| CN110755711A (en) * | 2019-10-31 | 2020-02-07 | 慧生医学科技(徐州)有限公司 | Photolysis-adhesion infusion patch |
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