Background technology
Medical conductive pressure sensitive adhesive is that one both had pressure-sensitive, possesses again the pressure sensitive adhesives of electroconductibility.So-called pressure-sensitive, refers to and does not rely on solvent, solution, just can realize a kind of binding agent bondd only by contact pressure, its main feature is easy to adhere to this pressure sensitive adhesive, can not leave residue simultaneously when stripping.So-called electroconductibility is that this pressure sensitive adhesives can be good at delivered current signal after boning with various medical equipment.
Along with the requirement of environment protection is more and more higher; because solvent type pressure-sensitive adhesive agent also exists some following problems: due to the toxic solvent contained in solvent pressure-sensitive adhesive; and inflammable, very large pollution is produced to environment, thus constrains the widespread use of solvent-borne type pressure sensitive adhesives.
Conventional emulsion polymerization technology there will be emulsion system heat because be difficult to transmit and cause gel cruelly poly-, and the emulsion polymerization technology of preparation adopts emulsifying agent and water as solvent, thus the letex polymerization pressure sensitive adhesive curing cycle prepared obtains prolongation, and it is low that operating efficiency becomes.
Along with the development of uv photopolymerization theory and the requirement of people to environmental protection more and more higher, thus more and more higher for the cry producing green product, photocuring is a kind of novel green technology, refer under the effect of light (Uv and visible light), liquid oligopolymer or monomer are through crosslinking polymerization thus the process of the solid product formed, thus achieve solvent-free discharge, not only safe but also do not pollute the environment, achieve curing speed fast, production efficiency is high, is applicable to the production of streamline.Need within several hours, just can complete for those thermofixations, photocuring only needs just can complete a few second.
Acrylate pressure-sensitive adhesive prepared by most uv photopolymerization technology all not can be good at solving acrylate pressure-sensitive adhesive tack, hold the difficult problem that viscosity, set time and volumetric shrinkage balance altogether, and the acrylate pressure-sensitive adhesive of great majority preparation hard and crisp, thus and be not suitable for industrialization and produce on a large scale hold viscosity extreme difference.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides medical conductive pressure sensitive adhesive of a kind of ultra-violet curing and preparation method thereof.
The present invention solves the technical scheme that its technical problem adopts: the medical conductive pressure sensitive adhesive of a kind of ultra-violet curing, by mass percentage, comprise following component: functional monomer 12 ~ 20%, soft monomer 12 ~ 20%, urethane acrylate 1 ~ 8%, linking agent 0.07 ~ 0.3%, ionogen 0.5 ~ 2%, NaOH0.5 ~ 2%, distilled water 12 ~ 15%, dehydrated alcohol 5 ~ 8%, PEG4009 ~ 12%, glycerine 22 ~ 32%, 1, 2-propylene glycol 2 ~ 4% and ultraviolet initiator 0.06 ~ 0.15%, wherein, functional monomer is vinylformic acid, methacrylic acid, one in 2-acrylamide-2-methyl propane sulfonic, soft monomer is β propyloic acrylic ester, 2-EHA, one in butyl acrylate.
The preparation method of the medical conductive pressure sensitive adhesive of ultra-violet curing, comprises the following steps: ultraviolet initiator, urethane acrylate, linking agent and dehydrated alcohol are added in A beaker, stirring and dissolving; Add in B beaker by ionogen, NaOH, distilled water, stirring and dissolving, adds functional monomer, soft monomer, PEG400, glycerine and 1,2-PD in B beaker, stirring and dissolving again; By the liquid mixing in two beakers together, leave standstill 1 ~ 2 hour after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 5 ~ 20 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Further, linking agent is N,N methylene bis acrylamide, and ionogen is KCl, NaCl or NH
4cl, ultraviolet initiator is benzoin dimethylether.
Further, the preparation method of urethane acrylate is: add in reaction vessel by polyether glycol, vulcabond and catalyzer, 60 ~ 80 DEG C are reacted 2 ~ 3 hours, slowly esters of acrylic acid end-capping reagent is instilled again in reaction vessel, 80 ~ 100 DEG C are reacted 10 ~ 12 hours, obtain urethane acrylate.
Further, polyether glycol is the one in polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran, vulcabond is 2, one in 4-tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate, end-capping reagent is hydroxyethyl methylacrylate or Hydroxyethyl acrylate, catalyzer is organo-bismuth, the mol ratio of polyether glycol, vulcabond and end-capping reagent is (0.02 ~ 0.05): (0.05 ~ 0.12): (0.06 ~ 0.13), and the content of catalyzer is 0.1 ~ 0.2% of polyether glycol and vulcabond total content.
Further, polyether glycol is polypropylene glycol, and vulcabond is 2,4 toluene diisocyanate.
Urethane acrylate, soft section specifically has the polypropylene glycol, polytetrahydrofuran etc. of different molecular weight, urethane acrylate macromole contains two double bonds due to end, can play the effect of macromolecules cross-linking agent, thus it can play good regulating effect to the force of cohesion of pressure sensitive adhesive and cohesive force; Urethane acrylate and N,N methylene bis acrylamide, under the irradiation of UV-light, increase the intensity of pressure sensitive adhesive; Small molecules ionogen, gives the conductive capability of the pressure sensitive adhesive after ultraviolet light polymerization; NaOH, for the part acid in neutralization solution, improves the pH value of solution, controls 5 ~ 7 by the pH value of the conductive pressure sensitive adhesive after solidification; Distilled water as solvent, for dissolving the compounds such as KCl, NaOH; Dehydrated alcohol is as also having sterilization while solvent, increasing the effect of cohesive force; PEG400 plays the wet performance keeping conductive pressure sensitive adhesive, and plays plasticization effect, and PEG400, glycerine and 1,2-PD are as the sticky humidity and the cohesive force that increase solution while solvent.
The invention has the beneficial effects as follows: some defects solving traditional solvent pressure-sensitive adhesive, letex polymerization type pressure sensitive adhesive, improve working efficiency; Urethane acrylate can prepare force of cohesion and the very large conductive pressure sensitive adhesive of cohesive force difference due to the change of added amount, and the change served only by the percentage composition of macromolecules cross-linking agent just can regulate the viscosity of pressure sensitive adhesive; Conductive pressure sensitive adhesive has no pungency to skin, is that a kind of biocompatibility is good, a kind of hydrogel of swelling behavior excellence, and this medical conductive pressure sensitive adhesive solve before pressure sensitive adhesive there will be the defects such as dry, storage time is short, heat resistance is poor.
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
By 0.02mol polypropylene glycol (Mn=400), 0.05mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.1% of 4-tolylene diisocyanate total mass, 60 DEG C are reacted 2 hours, in reaction vessel, slowly instill 0.06mol hydroxyethyl methylacrylate again, 80 DEG C are reacted 10 hours, obtain urethane acrylate.
In mass ratio, 0.08% benzoin dimethylether, 2% urethane acrylate, 0.08%N, N-methylene-bisacrylamide and 7% dehydrated alcohol are added in A beaker, stirring and dissolving; 1.5%KCl, 1.7%NaOH, 12% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 15% vinylformic acid, 15% β propyloic acrylic ester, 12%PEG400,3%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 1 hour after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 15 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Embodiment 2
By 0.04mol polypropylene glycol (Mn=400), 0.08mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.2% of 4-tolylene diisocyanate total mass, 80 DEG C are reacted 3 hours, in reaction vessel, slowly instill 0.1mol hydroxyethyl methylacrylate again, 80 DEG C are reacted 12 hours, obtain urethane acrylate.
In mass ratio, 0.07% benzoin dimethylether, 1% urethane acrylate, 0.09%N, N-methylene-bisacrylamide and 7% dehydrated alcohol are added in A beaker, stirring and dissolving; 2%KCl, 1.5%NaOH, 15% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 16% vinylformic acid, 20% β propyloic acrylic ester, 10%PEG400,4%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 1 hour after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 10 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Embodiment 3
By 0.02mol polypropylene glycol (Mn=400), 0.05mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.1% of 4-tolylene diisocyanate total mass, 60 DEG C are reacted 3 hours, in reaction vessel, slowly instill 0.07mol hydroxyethyl methylacrylate again, 100 DEG C are reacted 10 hours, obtain urethane acrylate.
In mass ratio, 0.08% benzoin dimethylether, 3% urethane acrylate, 0.07%N, N-methylene-bisacrylamide and 8% dehydrated alcohol are added in A beaker, stirring and dissolving; 1.5%KCl, 1.2%NaOH, 12% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 20% vinylformic acid, 14% β propyloic acrylic ester, 12%PEG400,4%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 1 hour after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 15 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Embodiment 4
By 0.02mol polypropylene glycol (Mn=400), 0.06mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.1% of 4-tolylene diisocyanate total mass, 80 DEG C are reacted 2 hours, in reaction vessel, slowly instill 0.09mol Hydroxyethyl acrylate again, 100 DEG C are reacted 10 hours, obtain urethane acrylate.
In mass ratio, 0.09% benzoin dimethylether, 1.2% urethane acrylate, 0.07%N, N-methylene-bisacrylamide and 8% dehydrated alcohol are added in A beaker, stirring and dissolving; 1.5%KCl, 1.5%NaOH, 12% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 18% vinylformic acid, 18% β propyloic acrylic ester, 12%PEG400,4%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 2 hours after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 20 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Embodiment 5
By 0.02mol polypropylene glycol (Mn=400), 0.05mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.1% of 4-tolylene diisocyanate total mass, 80 DEG C are reacted 3 hours, in reaction vessel, slowly instill 0.07mol Hydroxyethyl acrylate again, 80 DEG C are reacted 12 hours, obtain urethane acrylate.
In mass ratio, 0.08% benzoin dimethylether, 4% urethane acrylate, 0.09%N, N-methylene-bisacrylamide and 8% dehydrated alcohol are added in A beaker, stirring and dissolving; 0.5%KCl, 1%NaOH, 13% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 20% vinylformic acid, 16% β propyloic acrylic ester, 10%PEG400,4%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 2 hours after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 10 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Embodiment 6
By 0.02mol polypropylene glycol (Mn=400), 0.06mol2,4-tolylene diisocyanate and organo-bismuth add in reaction vessel, the quality of organo-bismuth is polypropylene glycol and 2,0.1% of 4-tolylene diisocyanate total mass, 60 DEG C are reacted 3 hours, in reaction vessel, slowly instill 0.06mol Hydroxyethyl acrylate again, 80 DEG C are reacted 12 hours, obtain urethane acrylate.
In mass ratio, 0.07% benzoin dimethylether, 2.4% urethane acrylate, 0.07%N, N-methylene-bisacrylamide and 7% dehydrated alcohol are added in A beaker, stirring and dissolving; 0.9%KCl, 1.3%NaOH, 12% distilled water are added in B beaker, stirring and dissolving, add the glycerine of 16% vinylformic acid, 16% β propyloic acrylic ester, 12%PEG400,4%1,2-propylene glycol and surplus in B beaker again, stirring and dissolving; By the liquid mixing in two beakers together, leave standstill 1 hour after stirring, obtain the mixing solutions of clear; Mixing solutions is coated on PET film sheet, irradiates 15 seconds under ultraviolet light, obtain the medical conductive pressure sensitive adhesive of ultra-violet curing.
Pressure sensitive adhesive binding agent has three relatively important performance index: hold tack, initial bonding strength, stripping strength, and wherein stripping strength is most important, and we mainly measure initial bonding strength and the stripping strength of the conductive pressure sensitive adhesive of embodiment, and concrete data see the following form:
|
Maximum peeling force (N) |
Average peel force (N) |
Falling sphere is tested |
Resistance (M Ω) |
Embodiment 1 |
4.82 |
3.02 |
No. 20 balls |
0.07 |
Embodiment 2 |
5.04 |
3.12 |
No. 22 balls |
0.04 |
Embodiment 3 |
3.44 |
2.24 |
No. 16 balls |
0.07 |
Embodiment 4 |
4.57 |
2.87 |
No. 20 balls |
0.09 |
Embodiment 5 |
3.36 |
2.01 |
No. 16 balls |
0.16 |
Embodiment 6 |
5.17 |
3.36 |
No. 25 balls |
0.10 |